JP2019518104A - Coatings containing polyester macromers containing 1,1-dicarbonyl substituted 1-alkenes - Google Patents

Abstract

a) One or more polyester macromers containing one or more chains of residues of one or more diols and one or more diesters, wherein the residues of one or more diols and one or more diesters are Alternating along the chain, wherein a portion of the diester is 1,1-diester-1-alkene and at least one terminus comprises one residue of 1,1-diester-1 alkene, one or more A composition comprising: a polyester macromer, which may contain residues of one or more diols; and b) one or more polymers having a pendant Michael addition reaction donor group. Disclosed are coatings prepared from these compositions.

Description

  Disclosed are novel compositions containing polyester macromers containing residues of 1,1-diester-1-alkene compounds, and polymers containing pendant Michael addition reaction donors. Further disclosed are coatings containing the composition, and methods for using the composition as a coating.

  Polyesters are utilized in several applications because of their properties and ease of synthesis. Typical applications include coatings, coatings, fibers, and resins. Because of their properties, polyesters are also utilized in blends with other polymers in order to improve certain property limitations of other polymers. Such polymers include polycarbonates, polyamides, styrene polymers, and polyolefins. Polyesters are typically prepared by reacting diacids with dialcohols and are generally linear in structure. Crosslinking these polyesters is somewhat cumbersome due to their structure. Some crosslinking processes require special catalysts or high temperatures.

  1,1-Diester-1-alkenes, such as methylene malonate, contain two diester groups and an alkylene group located between the two diester groups. Recent developments in the synthesis of these compounds facilitate their synthesis and their use in various applications. See Malofsky, US 8,609,885; US 8,884,051; and US 9,108,914, which are incorporated herein by reference in their entirety for all purposes. Processes for transesterification of these compounds have also been recently developed. Malofsky et al. WO 2013/059473 and US 2014/0329980 (herein incorporated by reference in their entirety for all purposes) disclose the preparation of polyfunctional methylene malonates according to a plurality of synthetic schemes. One disclosed process involves reacting methylene malonate with a polyol in the presence of a catalyst to prepare a compound, wherein at least one of the ester groups on the methylene malonate is transesterified And react with the polyol to form a multifunctional compound (multifunctional means that there are two or more methylene malonate core units). The use of enzyme catalysis is disclosed. Sullivan, US 9,416,091 discloses transesterification of 1,1-disubstituted-1-alkenes using certain acid catalysts (herein incorporated by reference in its entirety for all purposes). It has been incorporated).

  A common application filed on August 11, 2016 entitled "POLYESTER MACROMERS CONTAINING 1, 1-DICARBONYL-SUBSTITUTED 1 ALKENES" of application No. 15/234, 191 is problematic Polyester macromers containing 1,1-dicarbonyl-substituted mono-alkenes useful for the preparation of polyester-containing compositions which can be crosslinked neatly without the need for catalysts and which can use relatively mild conditions It discloses about the composition to contain. Disclosed are coatings prepared from such compositions that exhibit enhanced properties, such as flexibility, adhesion to substrates, pencil hardness, solvent resistance, abrasion resistance, resistance to abrasion. UV resistance, acid resistance, base resistance and the like are included. Also disclosed are processes for preparing components for such coatings and the coatings. The disclosed compositions and processes result in significant improvements in coating technology. It is desirable to further enhance this technology to meet customer expectations.

  What is needed is a 1, 1-di useful for the preparation of a coating composition that can be neatly crosslinked without the need for problematic catalysts and that relatively mild conditions can be used. It is a composition containing a polyester macromer containing a carbonyl substituted 1 alkene. What is also needed is flexibility, adhesion to substrates, pencil hardness, solvent resistance, abrasion resistance, UV resistance, acid and base resistance at high temperatures, fuel resistance etc. Coatings prepared from such compositions that exhibit enhanced properties. There is a need for a process to prepare the coating.

U.S. Pat. No. 8,609,885 U.S. Pat. No. 8,884,051 U.S. Patent No. 9,108,914 International Publication No. 2013/059473 US Patent Application Publication No. 2014/0329980 U.S. Patent No. 9,416,091 U.S. Patent Application No. 15 / 234,191

式中、Ｚは、出現する度に別々に、−Ｒ^２ＯＨまたは−Ｒ^１であり；Ｒ^１は、出現する度に別々に、１つ以上のヘテロ原子を含有してもよいヒドロカルビル基であり；Ｒ^２は、出現する度に別々に、酸素原子への２つ以上の結合を有するヒドロカルビレン基であり、ヒドロカルビレン基は、１つ以上のヘテロ原子を含有してもよく；ｃは、１以上の整数であり；ｎは、約１〜３の整数である。ｃは、約２〜約８、または約３〜約６の整数であってもよい。ポリエステルマクロマーは、１つ以上のジオール及び１つ以上のジエステルの残基の１本の鎖を含有してもよく、ジエステルの少なくとも一部分は、１，１−ジエステル−１−アルケンである。開示するポリエステルマクロマーは、約４００、約６００、または約７００〜約３０００の数平均分子量を呈する。 Disclosed are: a) one or more polyester macromers containing one or more chains of residues of one or more diols and one or more diesters, the one or more diols and one or more diols The residues of the diester alternate along the chain, wherein a portion of the diester is 1,1-diester-1-alkene and at least one end is one residue of 1,1-diester-1-alkene A polyester macromer, wherein one or more of the ends may comprise residues of one or more diols; and b) one or more polymers having a pendant Michael addition reaction donor group. The pendant Michael addition reaction donating group may contain a functional group containing an active hydrogen atom. One or more polymers having a pendant type Michael addition reaction donating group are one or more of acrylic polyol, amine modified acrylic polyol, polycarbonate polyol, modified acrylic copolymer polyol, polyether amine, polyester polyol, polyether polyol, and siloxane polyol May be included. The composition may contain three or more chains of alternating residues of one or more diols and one or more diesters, at least a portion of the diesters being 1,1-diester-1-alkenes And each of the chains is attached at one end to the oxygen of the residue of a polyol having three or more oxygen atoms. Polyester macromers may correspond to Formula 1:

Wherein Z is -R ² OH or -R ¹ separately at each occurrence; R ¹ is a hydrocarbyl group that may contain one or more heteroatoms at each occurrence separately R ² is a hydrocarbylene group having two or more bonds to the oxygen atom, with each occurrence separately, which hydrocarbylene group may contain one or more heteroatoms; c is an integer of 1 or more; n is an integer of about 1 to 3. c may be an integer of about 2 to about 8, or about 3 to about 6. The polyester macromer may contain one chain of residues of one or more diols and one or more diesters, at least a portion of the diesters being 1,1-diester-1-alkenes. The disclosed polyester macromers exhibit a number average molecular weight of about 400, about 600, or about 700 to about 3000.

  The one or more diesters may comprise 1,1-diester-1-alkenes. In addition to the one or more 1,1-diester-1-alkenes, the one or more diesters may include one or more dihydrocarbyl dicarboxylates. The polyester macromer may contain residues of one or more 1,1-diester-1-alkenes, as well as one or more residues of dihydrocarbyl dicarboxylates. One or more dihydrocarbyl dicarboxylates are aromatic dicarboxylates, aliphatic carboxylates, alicyclic carboxylates, and / or two different hydrocarbyl groups selected from aromatic, aliphatic and alicyclic. May contain one or more carboxylates containing

  Disclosed are: i) a plurality of polyester macromers as described herein; ii) one or more containing residues of one or more polyols and one or more 1,1-diester-1-alkenes A multifunctional monomer, wherein substantially all of the hydroxyl groups of the polyol of the multifunctional monomer are replaced with 1,1-diester-1-alkenes; and iii) one or more A composition comprising a polyester macromer composition comprising a 1,1-diester-1-alkene of The one or more polyols may be diols. The one or more multifunctional monomers may be difunctional monomers. The composition may be combined with one or more polymers having pendant Michael addition reaction donating groups.

  Disclosed are: a) i) a plurality of polyester macromers as described herein; ii) containing residues of one or more polyols and one or more 1,1-diester-1-alkenes 1 One or more multifunctional monomers, wherein substantially all of the hydroxyl groups of the polyol of the multifunctional monomer are replaced by 1,1-diester-1-alkenes; and iii) 1 Polyester macromer compositions comprising two or more 1,1-diester-1-alkenes; b) volatile solvents; c) additional amounts of one or more 1,1-diester-1-alkenes, if desired; d) one or more leveling agents and wetting agents; e) one or more UV stabilizers; f) one or more additives to improve the abrasion resistance; and g) surface slip and dent resistance Bring One or more additives is a composition containing. The solvent may be an alkoxyalkanol or alkoxyalkyl acetate. The wetting agent may be a polyether modified polydimethylsiloxane. The UV stabilizer may be a benzotriazole or hindered amine compound. The composition may contain an additive to improve scratch resistance, which may be a nanometer sized silica filler. The additive for improving surface slip may be polyether modified polydimethylsiloxane. The composition may be combined with one or more polymers having pendant Michael addition reaction donating groups.

  Disclosed are one or more polyester macromers and polyols terminated with one or more 1,1-diester-1-alkenes or multifunctional monomers (ie, one or more of the chain ends is one). , 1-diester-1-alkene and / or containing residues of multifunctional monomers). The composition may contain a solvent. The one or more polyols may be one or more polyether polyols, polysiloxane polyols, polycarbonate polyols, polyester polyols, acrylic polyols, or polybutadiene polyols. The one or more polyols may be one or more polycarbonate polyols. One or more polyols may be di- or trifunctional. One or more polyols may have Michael donating groups, such as hydroxyl, thiol, or amino groups, pendant from their backbone.

  Compositions containing the polyester macromers and one or more polymers having pendant Michael addition reaction donating groups disclosed herein may be processed into films or coatings. The coating or coating may have a thickness of about 0.001 micrometer or more, or about 10 micrometers or more. The coating or coating may have a thickness of about 160 micrometers or less or about 140 micrometers or less. Compositions comprising a plurality of one or more polyester macromers disclosed herein and one or more polymers having pendant Michael addition reaction donating groups may be cured. Compositions containing one or more of the polyester macromers disclosed herein may be crosslinked after curing.

  Disclosed are compositions comprising a) a plurality of polyester macromers as described above and b) one or more polymers having pendant Michael addition reaction donor groups, wherein part or all of the polyester macromers are 1, 1 A composition which is crosslinked via an alkene group. Disclosed are compositions comprising a) a plurality of polyester macromers as described above and b) one or more polymers having pendant Michael addition reaction donor groups, wherein the Michael addition reaction donor is pendant from the polymer A composition in which part or all of the polyester macromer is crosslinked by the Michael addition reaction to one alkene group of the polyester macromer.

  Disclosed are one or more polyester macromers as disclosed herein in the first part, and one or more basic enough to initiate anionic polymerization of the polyester macromer in the second part. A composition wherein the polyester macromer is cured when the two parts are combined. The one or more compounds having basicity may contain one or more amines or polyamines. The one or more compounds having basicity may comprise one or more polyalkyleneimines. These compositions may be combined with one or more polymers having pendant Michael addition reaction donating groups.

  Disclosed is an article having a coating comprising, as part of the composition, one or more polyester macromers and one or more polymers having pendant Michael addition reaction donating groups, the article comprising one of the surfaces It is an article in which the coating is disposed on all or part of the above. The article may have a basecoat onto which the coating formulation may be deposited. The base coat may contain a dye. The base coat may have a basic pH on the surface. The dyes may be basic. The base coat may have amine or hydroxyl groups on the surface that can help the curing process and adhesion of the coating to the substrate. The polyester macromer coating may be transparent. The polyester macromer coating may contain dyes or other known components used in the coating.

  Disclosed is contacting a composition according to the above containing at least one polyester macromer and at least one polymer having a pendant Michael addition reaction donor with the surface of a substrate, which is at least weakly basic. As well as forming on the surface of the substrate a coating comprising a composition containing one or more polyester macromers. The substrate may be composed of one or more of at least weakly basic, nucleophilic and / or materials containing multiple Michael addition reaction donor groups on its surface.

  Disclosed are compositions that are at least weakly basic, and are nucleophilic, comprising at least a composition comprising one or more polyester macromers and one or more polymers having pendant Michael addition reaction donor groups as disclosed herein. Contacting the surface of the substrate containing the agent and / or the Michael addition reaction donor, and forming a coating on the surface. The substrate may be composed of one or more of materials that are at least weakly basic, nucleophilic, and / or that contain a Michael addition reaction donor group. An anionic polymerization of the polyester macromer 1, 1-disubstituted alkene is initiated prior to applying the composition containing one or more polyester macromer and macromer and one or more polymer having pendant Michael addition reaction donor groups. Alternatively, a composition containing a basic, nucleophilic, or Michael addition reaction donor compound that is Michael added to an alkene group may be applied to the surface of the substrate. Representative basic compounds include one or more amines, polyamines, basic dyes; polyalkyleneamines polyethylene amines, and carboxylates. A method for forming a coating comprises placing a substrate having a composition comprising one or more polyester macromers and one or more polymers having pendant Michael addition reaction donors on the surface of the substrate About 10 minutes to about 10 minutes at a temperature of about 20 ° C. to about 150 ° C., under conditions such that a coating containing one or more polyester macromers and one or more polymers having pendant Michael addition reaction donor groups is crosslinked It may further include exposing for 120 minutes. The coating may also be cured at ambient temperature without heat input, which requires longer cure times, for example up to about 24 hours.

  A composition containing a polyester macromer and one or more polymers having pendant Michael addition reaction donors can be used to prepare coating formulations that can be cured and crosslinked using relatively mild conditions . The polyester macromer allows the properties of the polyester-containing composition to be tailored to the purpose. In particular, the polyester macromer allows the preparation of polyester compositions with improved mechanical properties and elasticity. The cured coatings disclosed have the following properties: gloss of 50 GU or more at 20 ° according to ASTM D523-08; pencil hardness of 4 H or more according to ASTM D3363-00; resistance to friction of 80 or more times of methyl ethyl ketone according to ASTM D5402-93 Solventability; 80% or more mandrel flexibility according to ASTM D522-93; 4B or more according to ASTM D 3359-09 and 100% crosshatch adhesion, and acid resistance up to 70 ° C according to GMW 14701 and base resistance above 70 ° C Present one or more of The method of preparing the coatings and films allows for the efficient preparation of coatings having the above-described enhanced properties.

  The explanations and illustrations presented herein are intended to acquaint others skilled in the art with the invention, its principles, and its practical application. The particular embodiments of the invention described above are not intended to be exhaustive or to limit the invention. The scope of the present disclosure should be determined in light of the attached claims and the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and references, are incorporated by reference for all purposes. Other combinations are possible as derived from the appended claims, which are also incorporated herein by reference.

  Unless defined otherwise, all technical and scientific terms used herein have meanings as commonly understood by one of ordinary skill in the art. The following references provide those skilled in the art with a general definition of the many terms used in this disclosure: Singleton et al. Dictionary of Microbiology and Molecular Biology (2nd ed. 1994); The Cambridge Dictionary of Science and Technology (Walker ed., 1988); The Glossary of Genetics, 5th Ed. , R. Rieger et al. (Eds.), Springer Verlag (1991); and Hale & Marham, The Harper Collins Dictionary of Biology (1991). The following terms have the meanings given to them below unless otherwise indicated.

  Disclosed are: a) Polyester macromers containing residues of one or more diols and one or more diesters in one or more chains, which residues of one or more diols and one or more diesters Are alternately present along the chain, part of the diester being 1,1-diester-1-alkene, at least one end comprising one residue of 1,1-diester-1-alkene, one A composition comprising a polyester macromer, and b) one or more polymers having a pendant Michael addition reaction donor group, wherein the above ends may comprise one or more diol residues. Macromers may have more than one such chain. The chain may comprise one or more residues of dihydrocarbyl dicarboxylate. The chain may contain residues of one or more diols and one or more diesters, the diesters comprising one or more 1-diester-1-alkenes, one or more diols and one The residues of the above 1,1-diester-1 alkene and optionally one or more dihydrocarbyl dicarboxylates may be randomly arranged along the chain. Polyester macromers can be used to form polyesters blended with polyesters and / or other macromolecular compounds to enhance properties. Disclosed are methods of preparing polyester macromers and incorporating them into various polyester-containing compositions. Further disclosed are methods of preparing structures such as coatings from polyester macromer-containing compositions.

  As used herein, diester refers to any compound having two ester groups that can be transesterified. A 1,1-diester-1-alkene is a compound containing two ester groups and a double bond attached to a single carbon atom called one carbon atom. The dihydrocarbyl dicarboxylate is a diester having a hydrocarbylene group between ester groups, and a double bond is not bonded to a carbon atom bonded to two carbonyl groups of the diester.

  The term "monofunctional" refers to 1,1-diester-1-alkenes having only one core unit. The core unit comprises two carbonyl groups and a double bond bonded to a single carbon atom. The term "difunctional" refers to 1,1 having two core units (each containing a reactive alkene functional group) linked through a hydrocarbylene linkage between one oxygen atom of each of the two core formulas -Refers to diester-1-alkene. The term "multifunctional" refers to two or more core units linked through hydrocarbylene linkages between one oxygen atom of each of two or more core formulas (each core unit is a reactive alkene functional group And the like) refers to 1,1-diester-1-alkenes.

  An acid catalyst, as used herein, is an acidic species that catalyzes a transesterification reaction with minimal or no side reaction. "One or more" as used herein means that at least one, or two or more of the listed components can be used as disclosed. The nominal used for functionality refers to the theoretical functionality, which can generally be calculated from the stoichiometry of the components used. Heteroatoms refer to atoms that are not carbon or hydrogen, such as nitrogen, oxygen, sulfur and phosphorus. Heteroatoms may include nitrogen and oxygen. Hydrocarbyl, as used herein, refers to a group containing a backbone of one or more carbon atoms and a hydrogen atom, which may optionally contain one or more heteroatoms. If the hydrocarbyl group contains a heteroatom, the heteroatom may form one or more functional groups well known to those skilled in the art. The hydrocarbyl group may contain alicyclic, aliphatic, aromatic or any combination of such segments. The aliphatic segment may be linear or branched. Aliphatic and cycloaliphatic segments may contain one or more double and / or triple bonds. Included in the hydrocarbyl groups are alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, alkaryl and aralkyl groups. Alicyclic groups can contain both cyclic and acyclic moieties. Hydrocarbylene means hydrocarbyl groups having a valence of 2 or more or any of the subsets described, such as, for example, alkylene, alkenylene, alkynylene, arylene, cycloalkylene, cycloalkenylene, alkarylene, and aralkylene. Weight percent or parts by weight, as used herein, unless otherwise indicated, refers to or is based on the weight of the described compound or composition. Unless otherwise stated parts by weight are based on 100 parts of the relevant composition.

  The term "ketal" refers to a molecule having a ketal functional group, ie, a molecule containing carbon linked to two -OR groups, where O is oxygen and R represents any alkyl group or hydrogen. Point to The term "volatile" refers to compounds that can be readily evaporated at ambient temperature and pressure. "Nonvolatile" refers to compounds that can not be readily evaporated at ambient temperature and pressure. The term "stabilized" (eg, in the context of "stabilized" 1,1-diester-1-alkene or a composition comprising the same) does not substantially polymerize over time, but over time Do not solidify, do not form gels, do not concentrate or do not increase in viscosity, and / or substantially exhibit minimal loss of cure rate over time (ie, cure rate is maintained) , The tendency of compounds (or their composition). The residues for the components used to prepare the polyester macromers disclosed herein are components (polyols such as diols, 1) which remain in the compound after being included as a result of the methods disclosed herein. , 1-diester-1-alkene and / or a diester such as dihydrocarbyl dicarboxylate etc.). "Substantially all" as used herein refers to a parameter, composition or compound of the referenced parameter, composition or compound which meets more than 95% of the defined criteria. More than 99% meets the defined criteria or means that more than 99.5% of the referenced parameter, composition, or compound meets the defined criteria.

  Disclosed are polyester macromers containing one or more chains containing residues of one or more diols and one or more diesters, wherein a portion of the diesters is 1,1-diester-1-alkene And polyester macromer. Residues of diols and diesters may alternate along the chain or may be randomly arranged along the chain. The diester may further comprise any diester compound that is transesterified with a polyol or diol. The diester compounds include dihydrocarbyl dicarboxylate. The polyester macromer may have three or more chains as described. Polyester macromers having three or more chains originally contain residues of polyols having three or more hydroxyl groups. Three or more chains respectively extend from three or more hydroxyl groups. Polyols having three or more chains function as initiators, from which polyester macromer chains respectively extend. If the polyol is a diol, then the macromer formed is linear, thus producing a single chain. When a polyol having three or more hydroxyls is used to prepare a macromer, the macromer may have two or more chains because not all of the hydroxyls can extend the chain. The macromer may contain one or more chains, two or more chains, or three or more chains. The macromer may contain 8 or less chains, 6 or less chains, 4 or less chains, or 3 or less chains. The chain comprises one or more polyols, one or more diols, and one or more diesters (one or more 1,1-diester-1-alkenes, and optionally one or more dihydrocarbyl dicarboxylates. And the like) may be included. The chain is the residue of one or more diols and one or more diesters (including one or more 1,1-diester-1-alkenes and optionally one or more dihydrocarbyl dicarboxylates) May be included. The polyester macromer contains at least one residue of 1,1-diester-1-alkene at one end of the chain. The polyester macromer may further comprise one or more diols or dihydrocarbyl dicarboxylates at one or more ends of the chains. Substantially all of the chain ends may be 1,1-diester substituted alkenes.

  The polyester macromer may contain residues of one or more polyols in an amount sufficient to initiate the desired number of chains. In this case, the polyol has three or more hydroxyl groups. The residue of the polyol in the polyester macromer may be about 20 mole percent or more, 30 mole percent or more, or about 40 mole percent or more of the macromer. The residue of the polyol in the polyester macromer may be about 50 mole percent or less, or about 40 mole percent or less. The polyester macromer may comprise a residue of one or more diols in an amount sufficient to prepare a polyester macromer having the desired chain length and number average molecular weight. In this case, the polyol has two hydroxyl groups. The residue of the diol in the polyester macromer may be about 20 mole percent or more, 40 mole percent or more, or about 50 mole percent or more of the macromer. The residue of the diol in the polyester macromer may be about 50 mole percent or less, 40 mole percent or less, or about 30 mole percent or less. The polyester macromer may comprise residues of 1,1-diester substituted 1-alkene in an amount sufficient to provide the desired crosslink density in the composition containing the polyester macromer. The residue of the 1,1-diester-substituted -1-alkene in the polyester macromer may be about 20 mole percent or more, 30 mole percent or more, or about 40 mole percent or more of the macromer. The residue of 1,1-diester substituted -1-alkene in the polyester macromer is less than about 60 mole percent of the macromer, less than about 50 mole percent of the macromer, less than about 40 mole percent, or less than about 30 mole percent. It is also good. The polyester macromer provides the composition containing the polyester macromer with the desired spacing during crosslinking to provide a sufficient amount of dihydrocarbyl dibasic to provide the desired structure with polyester macromer flexibility and / or elasticity. It may contain carboxylate residues. The residue of dihydrocarbyl dicarboxylate in the polyester macromer may be about 10 mole percent or more, 20 mole percent or more, or about 30 mole percent or more of the polyester macromer. The residue of dihydrocarbyl dicarboxylate in the polyester macromer may be about 30 mole percent or less, 20 mole percent or less, or about 10 mole percent or less of the polyester macromer.

式中、Ｚは、出現する度に別々に、−Ｒ^２ＯＨまたは−Ｒ^１であり、Ｒ^１は、出現する度に別々に、１つ以上のヘテロ原子を含有し得るヒドロカルビル基であり；Ｒ^２は、出現する度に別々に、酸素原子への２つ以上の結合を有するヒドロカルビレン基であり；ｃは、１以上の整数であり；ｎは、約１〜３の整数である。Ｒ^２に関して、酸素原子への結合は、Ｒ^２を使用する状況に応じて、ポリオール、ジオール、もしくはジエステル、またはそれらの残基の酸素への結合を含んでもよい。 Polyester macromers may correspond to Formula 1:

Wherein Z is -R ² OH or -R ¹ separately on each occurrence and R ¹ is a hydrocarbyl group which may contain one or more heteroatoms on each occurrence separately; R ² is a hydrocarbylene group having two or more bonds to an oxygen atom, each time separately occurring; c is an integer of 1 or more; n is an integer of about 1 to 3 . For R ² , attachment to an oxygen atom may include attachment of a polyol, diol, or diester, or their residue to oxygen, depending on the context of use of R ² .

式中、Ｚ、Ｒ^１、及びＲ^２は前に定義した通りであり；ｍは、約１〜３の整数である。 The polyester macromer may contain one chain of residues of one or more diols and one or more diesters. These polyester macromers may correspond to Formula 2:

Wherein Z, R ¹ and R ² are as defined above; m is an integer of about 1 to 3.

式中、Ｄは次式に相当し

A polyester macromer containing one or more residues of 1,1-diester-1-alkene and one or more residues of dihydrocarbyl dicarboxylate may correspond to one of the formulas 3 to 6;

Where D corresponds to

式中、Ｚ、Ｒ^１、Ｒ^２、及びｍは、前に定義した通りであり；Ｒ^３は、出現する度に別々に、状況に応じてジエステルの１つ以上のカルボニル基またはかかるジエステルの残基への２つの結合を有するヒドロカルビレン基であり、該ヒドロカルビレン基は、１つ以上のヘテロ原子を含有してもよく；ｃは、１または２以上の整数であり；ｄは、０または１の整数であり；ｅは、０または１の整数であり；ｆは、１の整数であり；ｎは、約１〜３の整数であり；ｐは、２以上の整数であり；ｑは、１以上の整数であり；ｄとｅの各対は１と等しくなければならない。ｐは、３以上の整数であってもよい。ｐは、８以下、６以下、または３以下の整数であってもよい。ｑは、４以下または３以下の整数であってもよい。 Where E corresponds to

Wherein Z, R ¹ , R ² and m are as defined above; R ³ is, each time separately, separately depending on the circumstances, one or more carbonyl groups of the diester or such diester A hydrocarbylene group having two bonds to a residue, which hydrocarbylene group may contain one or more heteroatoms; c is an integer of 1 or 2; d is , An integer of 0 or 1; e is an integer of 0 or 1; f is an integer of 1; n is an integer of about 1 to 3; p is an integer of 2 or more ; Q is an integer greater than or equal to 1; each pair of d and e must be equal to 1; p may be an integer of 3 or more. p may be an integer of 8 or less, 6 or less, or 3 or less. q may be an integer of 4 or less or 3 or less.

The polyester macromers may contain in their backbone repeating units comprising residues of at least one diester and one diol. A significant portion of the diester is 1,1-diester substituted 1-alkene. A portion of the diester may be 1,1-dihydrocarbyl dicarboxylate. The backbone of the polyester macromer contains a repeat unit comprising residues of at least one diester and one diol sufficient to facilitate the use of the polyester macromer as disclosed herein, eg coating etc. Do. The number of repeat units comprising residues of at least one diester and one diol in the polyester macromer may be 2 or more, 4 or more, or 6 or more. The number of repeat units comprising residues of at least one diester and one diol in the polyester macromer may be 8 or less, 6 or less, or 4 or less. The diesters in a polyester macromer may all be 1,1-diester-1-alkenes. The diesters in certain polyester macromers may be 1,1-diester-1-alkenes and dihydrocarbyl dicarboxylates. The molar ratio of 1,1-diester-1-alkene to dihydrocarbyl dicarboxylate in a polyester macromer is selected to provide the desired degree of crosslinking in structures prepared from the polyester macromer. The molar ratio of 1,1-diester-1-alkene to dihydrocarbyl dicarboxylate in a polyester macromer may be 1: 1 or more, 6: 1 or more, or 10: 1 or more. The molar ratio of 1,1-diester substituted 1-alkene to dihydrocarbyl dicarboxylate in a polyester macromer is 15: 1 or less, 10: 1 or less, 6: 1 or less, or 4: 1 or less. It is also good. The polyester macromer may exhibit a number average molecular weight of about 400 or more, about 600 or more, about 700 or more, about 900 or more, about 1000 or more, or about 1200 or more. The polyester macromer may exhibit a number average molecular weight of about 3000 or less, about 2000 or less, or about 1600 or less. Number average molecular weight, as used herein, is determined by dividing the total weight of all polymer molecules in a sample by the total number of polymer molecules in the sample. The polydispersity of the polyester macromer may be about 1.05 or more, or about 1.5 or more. The polydispersity of the polyester macromer may be about 2.5 or less, or about 1.5 or less. To calculate polydispersity, weight average molecular weight is determined using gel permeation chromatography using polymethyl methacrylate standards. The polydispersity is calculated by dividing the measured weight average molecular weight (M _v ) by the number average molecular weight (M _n ), ie M _v / M _n .

  The disclosed polyester macromers can be prepared from 1,1-diester-1-alkenes, diols, polyols, and / or dihydrocarbyl dicarboxylates. The choice of particular components, the ratio of components, and the order of the process steps influence the final structure and content of the polyester macromer. The presence of polyols having more than two hydroxyl groups functions to initiate chains, and their use results in the formation of polyester macromers having three or more chains. That is, the macromer is branched and the polymer is not linear. 1,1-Diester-1-alkenes help form chains and introduce pendant alkene groups that can be crosslinked via anionic and / or free radical polymerization and / or Michael addition reactions. The diol can initiate a single chain and can chain extend the polyester macromer. The dihydrocarbyl dicarboxylate functions to help form the chains and to space the pendant alkene groups away from one another, thereby increasing the distance between crosslinks and the average molecular weight per crosslink.

1,1-Diester-1-alkenes contain a central carbon atom called one carbon atom. Bonded to one carbon atom are the carbonyl groups of the two ester groups and another carbon atom via a double bond. The double bond is highly reactive because a carbon atom is bonded to two carbonyl groups. The double bonded carbon may be part of a highly reactive alkenyl group. The alkenyl group may be a _C2-4 alkenyl group or a methylene group (C = C). The ester contains a hydrocarbyl group linked to oxygen linked to a carbonyl group, which hydrocarbyl group may contain one or more heteroatoms, including heteroatom containing functional groups. The hydrocarbyl group may be any hydrocarbyl group that can be transesterified under the conditions disclosed herein. The hydrocarbyl groups on the ester may be alkyl, alkenyl, cycloalkyl, heterocyclyl, alkylheterocyclyl, aryl, aralkyl, alkaryl, heteroaryl or alkheteroaryl, or even polyoxyalkylene, as they occur, as they occur separately. Preferably, or both hydrocarbyl groups may form a 5- to 7-membered cyclic or heterocyclic ring. The hydrocarbyl groups on the ester are, as they appear separately, C ₁ -C ₁₅ alkyl, C ₂ -C ₁₅ alkenyl, C ₃ -C ₉ cycloalkyl, C _2-20 heterocyclyl, C _3-20 alkheterocyclyl ), C _6-18 aryl, C _7-25 alkaryl, C _7-25 aralkyl, C _5-18 heteroaryl or C _6-25 alkyl heteroaryl, or polyoxyalkylene, or both hydrocarbyl groups Forms a 5- to 7-membered cyclic or heterocyclic ring. The listed groups may be substituted with one or more substituents that do not interfere with the transesterification reaction. Representative substituents include halo, alkylthio, alkoxy, hydroxyl, nitro, azide, cyano, acyloxy, carboxy or ester. The hydrocarbyl groups on the ester are, as they appear, separately, C ₁ -C ₁₅ alkyl, C ₃ -C ₆ cycloalkyl, C _4-18 heterocyclyl, C _4-18 alk heterocyclyl, C _6-18 aryl, C _{7 -25} alkaryl, _C7-25 aralkyl, _C5-18 heteroaryl or _C6-25 alkyl heteroaryl, or polyoxyalkylene. The hydrocarbyl groups on the ester may be C _{1 -4} alkyl separately as they occur. The hydrocarbyl groups on the ester may be methyl or ethyl separately as they occur. The hydrocarbyl groups on the ester may be the same for each ester group on the 1,1-diester-1-alkene compound. Representative compounds are dimethyl, diethyl, ethylmethyl, dipropyl, dibutyl, diphenyl and ethyl-ethyl gluconate malonate. The compounds may be dimethyl and diethyl methylene malonate. 1,1-Diester-1-alkenes are described in Malofsky et al. U.S. Pat. No. 8,609,885; 8,884,051; and US Pat. No. 9,108,914.

Ｒ^１は、出現する度に別々に、本明細書に開示する方法の条件下で置き換えるまたはエステル交換させることができる基である。Ｒ^１は、出現する度に別々に、アルキル、アルケニル、シクロアルキル、ヘテロシクリル、アルキルヘテロシクリル、アリール、アラルキル、アルカリル、ヘテロアリール、もしくはアルクヘテロアリール、またはポリオキシアルキレンであってもよく、あるいは両方のＲ^１が５〜７員の環式または複素環式環を形成する。Ｒ^１は、出現する度に別々に、Ｃ_１〜Ｃ_１５アルキル、Ｃ_２〜Ｃ_１５アルケニル、Ｃ_３〜Ｃ_９シクロアルキル、Ｃ_２〜２０ヘテロシクリル、Ｃ_３〜２０アルクヘテロシクリル、Ｃ_６〜１８アリール、Ｃ_７〜２５アルカリル、Ｃ_７〜２５アラルキル、Ｃ_５〜１８ヘテロアリールもしくはＣ_６〜２５アルキルヘテロアリール、またはポリオキシアルキレンであってもよく、あるいは両方のＲ^１が５〜７員の環式または複素環式環を形成する。列挙された基は、エステル交換反応を妨害しない１つ以上の置換基で置換されていてもよい。代表的な置換基として、ハロ、アルキルチオ、アルコキシ、ヒドロキシル、ニトロ、アジド、シアノ、アシルオキシ、カルボキシ、またはエステルが挙げられる。Ｒ^１は、出現する度に別々に、Ｃ_１〜Ｃ_１５アルキル、Ｃ_３〜Ｃ_６シクロアルキル、Ｃ_４〜１８ヘテロシクリル、Ｃ_４〜１８アルクヘテロシクリル、Ｃ_６〜１８アリール、Ｃ_７〜２５アルカリル、Ｃ_７〜２５アラルキル、Ｃ_５〜１８ヘテロアリールもしくはＣ_６〜２５アルキルヘテロアリール、またはポリオキシアルキレンであってもよい。Ｒ^１は、出現する度に別々に、Ｃ_１〜４アルキルであってもよい。Ｒ^１は、出現する度に別々に、メチルまたはエチルであってもよい。Ｒ^１は、１，１−置換アルケン化合物上のエステル基ごとに同一であっても異なっていてもよい。 The 1,1-diester-1-alkene compound may correspond to Formula 7:

R ¹ is a group which can be replaced or transesterified separately as it appears, under the conditions of the process disclosed herein. R ¹ may be alkyl, alkenyl, cycloalkyl, heterocyclyl, alkylheterocyclyl, aryl, aralkyl, alkaryl, heteroaryl or alkheteroaryl, or polyoxyalkylene, or both, as and when each is separately R ¹ forms a 5- to 7-membered cyclic or heterocyclic ring. R ¹ is C _{1 to} C ₁₅ alkyl, C _{2 to} C ₁₅ alkenyl, C _{3 to} C ₉ cycloalkyl, C _{2 to 20} heterocyclyl, C _{3 to 20} alk heterocyclyl, C _{6 to 18} each separately as they occur It may be aryl, C _7-25 alkaryl, C _7-25 aralkyl, C _5-18 heteroaryl or C _6-25 alkyl heteroaryl, or polyoxyalkylene, or both R ¹ are 5 to 7-membered Form a cyclic or heterocyclic ring. The listed groups may be substituted with one or more substituents that do not interfere with the transesterification reaction. Representative substituents include halo, alkylthio, alkoxy, hydroxyl, nitro, azide, cyano, acyloxy, carboxy or ester. R ¹ is C _{1 to} C ₁₅ alkyl, C _{3 to} C ₆ cycloalkyl, C _{4 to 18} heterocyclyl, C _{4 to 18 alkheterocyclyl} , C _{6 to 18} aryl, C _{7 to 25} alkaryl, as each occurrence separately , C _7-25 aralkyl, C _5-18 heteroaryl or C _6-25 alkyl heteroaryl, or polyoxyalkylene. Each occurrence of R ¹ may be C _{1 -4} alkyl, separately. R ¹ may be methyl or ethyl separately at each occurrence. R ¹ may be the same or different for each ester group on the 1,1-substituted alkene compound.

式中、Ｒ^１は、本明細書において前に述べた通りである。 One class of 1,1-substituted alkene compounds is methylene malonate which may correspond to Formula 8:

Wherein R ¹ is as previously described herein.

  1,1-Diester-alkenes can be prepared using methods that are sufficiently pure so that they can be incorporated into polymerized and / or crosslinkable polyester macromers. The purity of 1,1-diester-1-alkene is at least 70 mole percent, at least 80 mole percent, at least 90 mole percent of the polyester macromer containing 1,1-diester-1-alkene during the polymerization or curing process. It may be high enough so that 95 mole percent or more, or 99 mole percent or more can be converted to the polymer. The purity of 1,1-diester-1-alkene is at least about 85 mole percent, at least about 90 mole percent, at least about 93 mole percent, about 95 moles, based on the total number of moles of 1,1-diester-1-alkene. It can be greater than or equal to percent, greater than or equal to about 97 mole percent, or greater than or equal to about 99 mole percent. If the 1,1-diester-1-alkene comprises a similar 1,1-diester alkane, it may be up to about 10 mole percent or up to about 1 mole percent. The concentration of any impurities containing dioxane groups is about 2 mole percent or less, about 1 mole percent or less, about 0.2 mole percent or less, or about 2 mole percent or less, based on the total moles of 1,1-diester-1-alkene It may be 0.05 mole percent or less. The total concentration of any impurities having an alkene group replaced by a similar hydroxyalkyl group (eg, by the Michael addition reaction of water to the alkene) is based on the total number of moles of 1,1-diester-1-alkene It may be about 3 mole percent or less, about 1 mole percent or less, about 0.1 mole percent or less, or about 0.01 mole percent or less. 1,1-diester-1-alkenes are one or more (eg two) distilling reaction products or intermediate reaction products (eg reaction product or intermediate reaction product of formaldehyde source and malonic acid ester) It may be prepared by a process including the above steps).

ジオールは、式１０に相当し得る：

式中、Ｒ^２は、出現する度に別々に、ポリオールのヒドロキシル基への２つ以上の結合を有するヒドロカルビレン基である。Ｒ^２は、出現する度に別々に、アルキレン、アルケニレン、シクロアルキレン、ヘテロシクリレン、アルキルヘテロシクリレン、アリーレン、アラルキレン、アルカリーレン、ヘテロアリーレン、アルクヘテロアリーレン、またはポリオキシアルキレンであってもよい。Ｒ^２は、出現する度に別々に、Ｃ_１〜Ｃ_１５アルキレン、Ｃ_２〜Ｃ_１５アルケニレン、Ｃ_３〜Ｃ_９シクロアルキレン、Ｃ_２〜２０ヘテロシクリレン、Ｃ_３〜２０アルクヘテロシクリレン、Ｃ_６〜１８アリーレン、Ｃ_７〜２５アルカリーレン、Ｃ_７〜２５アラルキレン、Ｃ_５〜１８ヘテロアリーレン、Ｃ_６〜２５アルキルヘテロアリーレン、またはポリオキシアルキレンであってもよい。列挙された基は、エステル交換反応を妨害しない１つ以上の置換基で置換されていてもよい。代表的な置換基として、ハロ、アルキルチオ、アルコキシ、ヒドロキシル、ニトロ、アジド、シアノ、アシルオキシ、カルボキシ、またはエステルが挙げられる。Ｒ^２は、出現する度に別々に、エチレン、プロピレン、ブチレン、ペンチレン、ヘキシレン、２−エチルヘキシレン、ヘプチレン、２−メチル１，３−プロピレン、またはオクチレンなどの、Ｃ_２〜８アルキレン基であってもよい。代表的なＣ_３〜Ｃ_９シクロアルキレンとして、シクロヘキシレンが挙げられる。アルキレン基は、分岐状でも直鎖状でもよく、２炭素上にメチル基を有してもよい。好ましいアルカリーレンポリオールとして、−アリール−アルキル−アリール−（−フェニル−メチル−フェニル−または−フェニル−プロピル−フェニル−など）などの構造を有するポリオールが挙げられる。好ましいアルキルシクロアルキレンポリイルとして、−シクロアルキル−アルキル−シクロアルキル−（−シクロヘキシル−メチル−シクロヘキシル−または−シクロヘキシル−プロピル−シクロヘキシル−など）などの構造を有するものが挙げられる。ポリアルキレンオキシ基は、エチレン、プロピレン、またはブチレンのアルキレン基を有してもよく、ブチレン基は、ブチレンオキシドまたはテトラヒドロフランから誘導されてもよい。ｃは、８以下、６以下、４以下、または３以下の整数であってもよい。ｃは、２以上または３以上の整数であってもよい。 Polyols useful in the preparation of the polyester macromers disclosed herein are compounds having a hydrocarbylene group linked to two or more hydroxyl groups, which are esters of the ester compounds under transesterification conditions disclosed herein. It is a compound that may be capable of performing transesterification. Polyols useful herein fall into two groups. The first group is diols having two hydroxyl groups attached to the hydrocarbylene backbone, which function to both initiate and extend the chains of the polyester macromer. Polyols having more than two hydroxyl groups attached to the hydrocarbylene backbone function to initiate more than two chains. The diol also functions to extend three or more chains. The polyol may have 2 to 10 hydroxyl groups, 2 to 4 hydroxyl groups, or 2 to 3 hydroxyl groups. The skeleton of the polyol (including a diol) is alkylene, alkenylene, cycloalkylene, heterocyclylene, alkylheterocyclylene, arylene, aralkylene, alkarylene, heteroarylene, alkheteroarylene, or polyoxyalkylene. It is also good. The skeleton is C _{1 to} C ₁₅ alkylene, C _{2 to} C ₁₅ alkenylene, C _{3 to} C ₉ cycloalkylene, C _{2 to 20} heterocyclylene, C _{3 to 20} alkheterocyclylene, C _{6 to 18} arylene , C _7-25 alkylene, C _7-25 aralkylene, C _5-18 heteroarylene, C _6-25 alkyl heteroarylene, or polyoxyalkylene. The alkylene section may be linear or branched. The listed groups may be substituted with one or more substituents that do not interfere with the transesterification reaction. Representative substituents include halo, alkylthio, alkoxy, hydroxyl, nitro, azide, cyano, acyloxy, carboxy or ester. The backbone may be a C _2-10 alkylene group. The skeleton is C _2-8 such as ethylene, propylene, butylene, pentylene, hexylene, 2-ethylhexylene, heptylene, 2,2-methyl, 1,3-propylene, 2-methyl 1,3-propylene, or octylene. It may be an alkylene group, which may be linear or branched. A diol having a methyl group at the 2-position of the alkylene chain may be used. Representative diols include ethanediol, propanediol, butanediol, pentanediol, hexanediol, 2-ethylhexanediol, heptanediol, octanediol, neopentyl glycol (2,2-methyl, 1,3-propanediol), 2-methyl 1,3-propanediol, 2-butyl-1,3-propanediol, 2-ethyl-1,3-propanediol, and 1,4-cyclohexanol. The polyol may correspond to formula 9

The diol may correspond to Formula 10:

In the formula, R ² is a hydrocarbylene group having two or more bonds to the hydroxyl group of the polyol separately on each occurrence. R ² may be alkylene, alkenylene, cycloalkylene, heterocyclylene, alkylheterocyclylene, arylene, aralkylene, alkarylene, heteroarylene, alkheteroarylene, or polyoxyalkylene, as and when it occurs separately . R ² is C _{1 to} C ₁₅ alkylene, C _{2 to} C ₁₅ alkenylene, C _{3 to} C ₉ cycloalkylene, C _{2 to 20} heterocyclylene, C _{3 to 20 alkycyclylene} , each time they occur separately C _{having 6 to 18 arylene, C 7 to 25 alkarylene, C 7 to 25 aralkylene, C 5 to 18} heteroarylene _may be _{C 6 to 25} alkyl heteroarylene or polyoxyalkylene. The listed groups may be substituted with one or more substituents that do not interfere with the transesterification reaction. Representative substituents include halo, alkylthio, alkoxy, hydroxyl, nitro, azide, cyano, acyloxy, carboxy or ester. R ² is a C _2-8 alkylene group such as ethylene, propylene, butylene, pentylene, hexylene, 2-ethylhexylene, heptylene, 2-methyl 1,3-propylene or octylene separately as each occurrence It may be. Typical _C 3 -C ₉ cycloalkylene include cyclohexylene. The alkylene group may be branched or linear, and may have a methyl group on two carbons. Preferred alkylene polyols include polyols having a structure such as -aryl-alkyl-aryl- (such as -phenyl-methyl-phenyl- or -phenyl-propyl-phenyl-). Preferred alkyl cycloalkylenepolyyls include those having a structure such as -cycloalkyl-alkyl-cycloalkyl- (-cyclohexyl-methyl-cyclohexyl- or -cyclohexyl-propyl-cyclohexyl- and the like). The polyalkyleneoxy group may have an alkylene group of ethylene, propylene or butylene, and the butylene group may be derived from butylene oxide or tetrahydrofuran. c may be an integer of 8 or less, 6 or less, 4 or less, or 3 or less. c may be an integer of 2 or more or 3 or more.

式中、Ｒ^１は、前述の通りであり；Ｒ^３は、出現する度に別々に、ジエステルのカルボニル基への２つの結合を有するヒドロカルビレン基であり、該ヒドロカルビレン基は、１つ以上のヘテロ原子を含有してもよい。Ｒ^３は、出現する度に別々に、アリーレン、シクロアルキレン、アルキレン、またはアルケニレンであってもよい。Ｒ^３は、出現する度に別々に、Ｃ_８〜１４アリーレン、Ｃ_８〜１２シクロアルキレン、Ｃ_１〜１２アルキレン、またはＣ_２〜１２アルケニレンであってもよい。 One or more dihydrocarbyl dicarboxylates are compounds having two ester groups and having a hydrocarbylene group arranged between the ester groups. One or more dihydrocarbyl dicarboxylates may comprise one or more of aromatic dicarboxylates, aliphatic dicarboxylates, and alicyclic dicarboxylates, or one of the hydrocarbyl groups is aliphatic, alicyclic It may also contain one or more dihydrocarbyl dicarboxylates of the formula or aromatic, the other being selected from aliphatic, alicyclic or another class of aromatic group. One or more dihydrocarbyl dicarboxylates are aromatic dicarboxylates having 8 to 14 carbon atoms in the backbone, aliphatic dicarboxylates having 1 to 12 carbon atoms in the backbone, and 8 to 8 in the backbone It may contain one or more of the alicyclic dicarboxylates having 12 carbon atoms. One or more dihydrocarbyl dicarboxylates may be one or more malonates, terephthalates, phthalates, isophthalates, naphthalene-2,6-dicarboxylates, 1,3-phenylenedioxydiacetates, cyclohexane dicarboxylates, cyclohexanes It may comprise diacetate, diphenyl-4,4'-dicarboxylate, succinate, glutamate, adipate, azelate, sebacate, or mixtures thereof. The one or more dihydrocarbyl dicarboxylates may comprise one or more malonate, isophthalate, terephthalate, or sebacate. One or more dihydrocarbyl dicarboxylates may correspond to Formula 11:

In which R ¹ is as defined above; R ³ is a hydrocarbylene group having two bonds to the carbonyl group of the diester separately, each time they occur, said hydrocarbylene group being It may contain one or more hetero atoms. R ³ may be arylene, cycloalkylene, alkylene, or alkenylene, each occurrence of which is separate. R ³ is separately in time the _{occurrence, C 8 to 14 arylene, C 8 to 12 cycloalkylene,} it may be a _{C 1 to 12} alkylene or _{C 2 to 12} alkenylene,.

ジオールを使用して多官能性モノマーを開始する場合、それらは式１３に相当する；

式中、Ｒ^１、Ｒ^２、及びｃは、上文で定義した通りである。多官能性モノマーは、下文に開示する通りに、ならびにＭａｌｏｆｓｋｙ、ＵＳ２０１４／０３２９９８０及びＳｕｌｌｉｖａｎ、ＵＳ９，４１６，０９１（両方ともあらゆる目的のためのそれらの全体が本明細書に組み込まれている）に開示される通りに調製することができる。 Some of the methods for preparing polyester macromers involve the preparation of intermediate compounds. Some classes of intermediate compounds are multifunctional monomers. Multifunctional monomers can be prepared from 1,1-diester-1-alkenes and polyols, including diols. If the polyol has more than two hydroxyl groups, it is desirable to prepare the multifunctional monomer prior to chain extension. Multifunctional monomers include polyols in which at least two of the hydroxyl groups have been replaced by residues of 1,1-diester-1-alkenes. If more than two hydroxyl groups are present on the polyol, not all of the hydroxyl groups may react with the 1,1-diester-1-alkene. It is desirable that substantially all of the hydroxyl groups react with the 1,1-diester-1-alkene. The structural options discussed above for polyols and 1,1-diester-1-alkenes are also applicable to multifunctional monomers. When preparing polyfunctional monomers using polyols having three or more hydroxyl groups, they correspond to formula 12:

If diols are used to initiate multifunctional monomers, they correspond to formula 13;

Wherein R ¹ , R ² and c are as defined above. Multifunctional monomers are disclosed as disclosed below and in Malofsky, US 2014/0329980 and Sullivan, US 9, 416, 091, both of which are incorporated herein in their entirety for all purposes. It can be prepared as it is.

ジオール末端処理ジヒドロカルビルジカルボキシレートは、式１５に相当し得る；

式中、Ｒ^２、Ｒ^３、及びｃは、上文に記載した通りである。この場合、Ｒ^３のヒドロカルビレンは、ポリオール末端処理ジヒドロカルビルジカルボキシレート中のジエステルの残基のカルボニル基に結合している。 Another intermediate that may be used to prepare the polyester macromer is one or more compounds comprising one or more dihydrocarbyl dicarboxylates with the residue of a polyol (such as a diol) attached to each of the carbonyl groups is there. These compounds are sometimes referred to as polyol terminated dihydrocarbyl dicarboxylates. Some of them are sometimes referred to as diol-terminated dihydrocarbyl dicarboxylates. Each ester group of dihydrocarbyl dicarboxylate is transesterified to replace the hydrocarbyl group with a polyol such as a diol. The resulting polyol terminated dihydrocarbyl dicarboxylate has a terminal hydroxyl group. The polyol terminated dihydrocarbyl dicarboxylate may correspond to Formula 14;

The diol terminated dihydrocarbyl dicarboxylate may correspond to Formula 15;

Wherein R ² , R ³ and c are as described above. In this case, the R ³ hydrocarbylene is attached to the carbonyl group of the residue of the diester in the polyol-terminated dihydrocarbyl dicarboxylate.

  Polyester macromers can be used in compositions useful for the preparation of polymers and structures from such polymers. The composition can be constructed by blending the polyester macromer with the desired components. The composition can comprise or include a mixture of compounds formed in the preparation of the polyester macromer. Other components are added to the mixture of compounds formed in the preparation of the polyester macromer, designed to be used for the preparation of the polymer containing the polyester macromer or the preparation of the structure formed from the polymer or the polyester macromer The composition may be formed. One composition comprises: i) a plurality of polyester macromers as disclosed herein; ii) one or more polys containing residues of one or more polyols and one or more 1,1-diester-1-alkenes A functional monomer, wherein substantially all of the hydroxyl groups of the polyol of the polyfunctional monomer are replaced by 1,1-diester-1-alkenes; and iii) one or more of one , 1-diester-1-alkene. Each of these components is disclosed above. This composition can be taken from the reaction mixture formed when the polyester macromer is prepared. The resulting reaction mixture is subjected to a separation process such as distillation to remove one or more of the excess more volatile species, such as alcohol, polyol, or unreacted dihydrocarbyl dicarboxylate, etc. Desired component concentrations can be achieved. One or more of the listed compounds may be added to achieve the desired component concentration. With respect to the polyester macromer, plural means that there are several polyester macromer units which may be the same or different polyester macromer. The polyester macromer is present in an amount sufficient to prepare the desired polymer and structures therefrom and to introduce the desired level of crosslinking. Any one or more of the polyester macromers disclosed herein may be used in the composition. Polyester macromers may be utilized which contain one or more residues of dihydrocarbyl dicarboxylate in the backbone. The polyester macromer used in the composition may comprise the residue of one or more polyols and one or more 1,1-diester-1-alkenes. 1,1-Diester-1-alkene is present to function as a reactive diluent and to facilitate formation of a composition exhibiting a target viscosity. 1,1-Diester-1-alkenes can provide rapid reactivity in the formation of the polymer or structure being prepared. One or more multifunctional monomers are present to enhance the crosslinking of the polymer or structure being prepared. The components are present in amounts sufficient to fulfill their listed purposes. The plurality of polyester macromers are present in an amount of about 10 weight percent or more, about 30 weight percent or more, or about 60 weight percent or more of the composition. The plurality of polyester macromers are present in an amount of about 80 weight percent or less, about 70 weight percent or less, or about 40 weight percent or less of the composition. The multifunctional monomer is present in an amount of about 5 weight percent or more, about 10 weight percent or more, about 20 weight percent or more, or 30 weight percent or more of the composition. The multifunctional monomer is present in an amount of about 50 weight percent or less, about 40 weight percent or less, about 30 weight percent or less, or about 20 weight percent or less of the composition. The 1,1-diester-1-alkene is present in an amount of about 0 weight percent or more, about 1 weight percent or more, about 5 weight percent or more, about 10 weight percent or more, or about 20 weight percent or more of the composition. The 1,1-diester-1-alkene is present in an amount of about 40 weight percent or less, about 30 weight percent or less, or about 20 weight percent or less of the composition. The one or more polyols may be diols. The multifunctional monomer may be a difunctional monomer.

  i) a plurality of polyester macromers as disclosed herein; ii) one or more multifunctional monomers containing residues of one or more polyols and one or more 1,1-diester-1-alkenes A multifunctional monomer wherein substantially all of the hydroxyl groups of the polyol of the multifunctional monomer are replaced by 1,1-diester-1-alkenes; and iii) one or more 1,1-diester- Compositions containing 1-alkenes may be used as a basis for preparing additional compositions. The composition may be used in such other compositions in an amount sufficient to function as desired. The composition may be present in an amount of about 10 weight percent or more, about 20 weight percent or more, about 30 weight percent or more, about 60 weight percent or more, or about 70 weight percent or more of the composition to be formed. The composition may be present in an amount of about 80 weight percent or less, about 60 weight percent or less, or about 30 weight percent or less of the composition. Such compositions may contain volatile solvents. The volatile solvent may be any solvent that does not react with the components or does not interfere with the curing of the composition. The solvent may be volatile at about 50 ° C. or higher. The solvent may be a volatile polar solvent. The solvent may be a volatile polar aprotic solvent. The polar aprotic solvent may be volatilized away from the other components once the coating is applied to the substrate. Any polar aprotic solvent that volatilizes away from the other components once applied to the surface of the substrate may be utilized herein. The polar aprotic solvent may exhibit a boiling point of about 100 ° C. or more, about 110 ° C. or more, or about 130 ° C. or more. The polar aprotic solvent may exhibit a boiling point of about 200 ° C. or less, about 190 ° C. or less, or about 170 ° C. or less. The polar aprotic solvent may be an alkylene glycol ether, an acetate modified alkylene glycol ether, a ketone, or a mixture of any of these solvents, and the like. The volatile solvent is present in an amount sufficient to facilitate the use of the composition as desired. That is, the solvent facilitates delivery of the composition and allows wet out of the composition on the surface. The volatile solvent is present in an amount of about 0 weight percent or more, about 1 weight percent or more, about 5 weight percent or more, about 10 weight percent or more, or about 20 weight percent or more of the composition. The volatile solvent is present in an amount of about 50 weight percent or less, about 40 weight percent or less, about 20 weight percent or less, or about 10 weight percent or less of the composition. The composition formed may contain an additional amount of 1,1-diester-1-alkene. Additional 1,1-diester-1-alkene functions as a reactive diluent and is present in the composition formed to promote polymerization. The additional 1,1-diester-1-alkene is present in an amount of 0 weight percent or more, about 1 weight percent or more, about 5 weight percent or more, about 10 weight percent or more, or about 30 weight percent or more of the composition. May be The additional 1,1-diester-1-alkene may be present in an amount of about 50 weight percent or less, about 40 weight percent or less, or about 30 weight percent or less of the composition.

  The composition formed may further contain one or more wetting agents that facilitate the application of such composition to a substrate. Any wetting and / or leveling agent may be used that enhances the application of the composition to the substrate. Representative classes of wetting agents include polyether modified polydimethylsiloxanes, fluorinated hydrocarbons and the like. The wetting agent may be a polyether modified polydimethylsiloxane. Wetting agents and / or leveling agents are present in an amount sufficient to facilitate application of the composition to the substrate surface. The wetting agent may be present in an amount of about 0.01 weight percent or more, about 0.5 weight percent or more, or about 1 weight percent or more of the composition. The wetting agent may be present in an amount of about 5 weight percent or less, about 2 weight percent or less, or about 1 weight percent or less of the composition. The composition formed may further contain one or more UV stabilizers that inhibit the degradation of the structure containing the polyester macromer. Any UV stabilizer that inhibits degradation by exposure to ultraviolet light may be used. Representative classes of UV light stabilizers include benzophenones, benzotriazoles, and hindered amines (generally known as hindered amine light stabilizers (HALS)). Cyasorb UV-531 (2-hydroxy-4-n-octoxybenzophenone), Tinuvin 571 (2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methyl, as a representative UV light stabilizer Phenolic), branched and linear Tinuvin 1,2,3 (bis- (1-octyloxy-2,2,6,6, tetramethyl-4-piperidinyl) sebacate), and Tinuvin 765 (bis (1,2,2) 2,6,6-pentamethyl-4-piperidinyl) sebacate). The UV light stabilizer is present in an amount sufficient to enhance the long term durability of the composition containing the polyester macromer. UV light stabilizers are selected such that they do not affect stability or pot life by free radical polymerization via an alkene double bond, anionic polymerization, or premature polymerization by initiating or catalyzing a Michael addition reaction It should. The UV light stabilizers may be present in an amount of about 0.01 weight percent or more, about 0.1 weight percent or more, or about 0.2 weight percent or more of the composition. The UV light stabilizers may be present in an amount of about 5 weight percent or less, about 3 weight percent or less, about 2 weight percent or less, or about 1 weight percent or less of the composition. The composition may further comprise an antifoaming agent and / or a degassing agent. Compositions containing polyester macromers can foam during processing, which can cause problems with the surface and appearance of the coating. Any antifoam and / or degassing agent may be used that prevents foaming or bubble formation and does not adversely affect the properties of the composition. Representative antifoam agents are silicone antifoam agents, silicone-free antifoam agents, polyacrylate antifoam agents, mixtures thereof and the like. As representative antifoams, FOAM BLAST (TM) 20F, FOAM BLAST (TM) 30 silicone antifoam compounds available from Emerald, and FOAM BLAST (TM) 550 polyacrylate antifoam; TEGO AIREX from Degussa (Trademark) 920 polyacrylate antifoam and TEGO AIREX (trademark) 980, SILMER ACR (trademark) Di-10 and ACR (trademark) Mo-8 polydimethylsiloxane acrylate copolymer from Siltech Corporation, FOAMEX N (available from Degussa Or TEGO AIREXTM 900 silicone based antifoam, or BYKTM 1790 silicone additive free antifoam made by BYK Chemie. The antifoam / deaerator is present in the polyester macromer composition in an amount sufficient to prevent the formation of bubbles and / or foaming. If too much is used, adhesion to the desired surface and the adhesive may be adversely affected. The antifoam and / or degassing agent may be present in an amount of about 0.01 weight percent or more, about 0.05 weight percent or more, or about 0.1 weight percent or more based on the weight of the composition . The antifoam / deaerator may be present in an amount of about 2.0 weight percent or less, or about 1.0 weight percent or less, based on the weight of the composition.

  These compositions may contain additives to improve the scratch resistance. Any additive that improves scratch resistance may be utilized. Representative scratch resistant additives can include silicates, alumina, zirconia, carbides, oxides, nitrides, or any other filler with high hardness. Typical scratch resistance additives are alumina (eg alpha alumina), silica, zirconia, boron carbide, silicon carbide, cerium oxide, glass, diamond, aluminum nitride, silicon nitride, silicon oxide, yttrium oxide, titanium diboride, Aluminosilicates (i.e. "Zeeospheres" from 3M), titanium carbide, combinations thereof and the like can be mentioned. Representative scratch resistant additives may be silicates and alumina. Exemplary scratch resistant additives can include nanometer sized silica fillers. The scratch resistant additive may have a particle size of about 10 micrometers or less, or about 5 micrometers or less. The scratch resistant additive may be present in an amount sufficient to enhance the surface hardness and abrasion resistance of the coating, and in an amount such that a homogenous dispersion can be prepared. The scratch resistant additive may be present in an amount of about 0.1 weight percent or more, or about 0.5 weight percent or more of the composition. The scratch resistant additive may be present in an amount of about 5 weight percent or less, about 2 weight percent or less, or about 1 weight percent or less of the composition.

  These compositions may also contain additives to improve surface slip. Any known composition that improves surface slip may be used. Representative surface slip additives may be polyester modified polydimethylsiloxanes, waxes and the like. Representative waxes are those based on polyethylene, polytetrafluoroethylene, or polypropylene wax dispersions in acrylate monomers, such as EVERGLIDETM or S-395 or SST series products from Shamrock Technologies, or polyamide particles, For example, ORGASOL (trademark) from Arkema, or montan wax having a reactive acrylate group, such as CERIDUST (trademark) TP 5091 (Clariant), or CERAFLOUR (trademark) wax powder from Byk-Chemie can be mentioned. The wax may be in powder form having a particle size smaller than the desired thickness of the coating prepared from the composition. The maximum particle size may be about 30 microns or less, about 25 microns or less, about 20 microns or less, or about 15 microns or less. The wax may be highly crystalline. Representative waxes include polyethylene, polypropylene, polyamide, polytetrafluoroethylene, or blends and copolymers thereof. The wax may be crystalline polyethylene or polytetrafluoroethylene, or a blend of polyethylene and polytetrafluoroethylene. The surface slip additive may be present in an amount of about 0.1 weight percent or more, or about 0.5 weight percent or more of the composition. The surface slip additive may be present in an amount of about 5 weight percent or less, about 2 weight percent or less, or about 5 weight percent or less of the composition.

  The compositions disclosed herein contain one or more polymers having pendant Michael addition reaction donating groups. Any polymer having pendant Michael addition reaction donor groups that improves the properties of coatings prepared from compositions containing multiple polyester macromers may be used in the compositions disclosed herein. Michael addition reaction donors are functional groups that react with electrophilic unsaturated groups such as alkene groups on polyester macromers. The Michael addition reaction donor may be a functional group containing at least one active hydrogen atom. The Michael addition reaction donor group may comprise an amine, hydroxyl, thiol, or mixtures thereof. The Michael addition reaction donating group may comprise an amine and / or a hydroxyl. The polymer containing pendant Michael addition reaction donor groups can be any polymer backbone that facilitates the preparation of coatings having desired properties such as those described herein. It is desirable to enhance the outdoor resistance of the polymer in the form of gloss, flexibility, and improved UV resistance and moisture resistance of coatings prepared from polyester macromer compositions and polymers having pendant Michael addition reaction donating groups. . The polymer having a pendant type Michael addition reaction donating group may be an acrylic, polycarbonate, styrene acrylonitrile, siloxane polyester, or polyether backbone. Representative polymers having a pendant type Michael addition reaction donating group include one or more of acrylic polyol, amine modified acrylic polyol, polycarbonate polyol, modified acrylic copolymer polyol, seed oil polyol, polyether polyol, polyester polyol, and siloxane polyol It can be mentioned. The one or more polymers having a pendant type Michael addition reaction donating group include one or more acrylic polyols or amine-modified acrylic polyols and the like. The polymer containing a pendant Michael addition reaction donor group may comprise a compound containing a polyacrylate backbone prepared from one or more acrylate containing compounds, but at least one of the acrylate containing compounds is a Michael addition reaction donor For example, containing hydroxyl, amino or thiol groups. Such polymers can be prepared via free radical polymerization as known to those skilled in the art. Representative acrylate compounds containing a Michael donating group include hydroxyl ethyl methacrylate, butyl hydroxyacrylate, ethyl hydroxyacrylate and the like. Styrene acrylonitrile-based polymers containing Michael addition reaction donors can be prepared by reacting styrene, acrylonitrile, and polyalkylene oxides containing active hydrogen-containing functional groups such as amine, hydroxyl or thiol groups . The polyalkylene oxide may be polypropylene oxide. The active hydrogen-containing functional group may be amino or hydroxyl, or may be hydroxyl. Polycarbonate-based polymers containing a Michael addition reaction donor are (A) (i) phosgene, (ii) branched polyhydric alcohols having about 4 to 12 carbon atoms, and (iii) about 5 to 20 Reacting about 3 to 40 mole percent (based on the total amount of polyhydric alcohol) of linear polyhydric alcohol having carbon atoms in the presence of a solvent and in the absence of a catalyst at a temperature of about 60 ° C. to 100 ° C. And (B) contacting the amorphous polycarbonate product in the reaction mixture with a catalytic amount of a tertiary amine at reflux temperature for at least 30 minutes.

  Polymers containing pendant Michael addition reaction donating groups may have hydroxyl numbers that enhance the properties of coatings prepared from the disclosed compositions. The hydroxyl number of the polymer containing the pendant type Michael addition reaction donating group may be about 40 or more, about 60 or more, or about 100 or more, as measured by potassium number. The hydroxyl number of the polymer containing the pendant Michael addition reaction donating group may be about 220 or less, about 200 or less, or about 150 or less, as measured by potassium number. The hydroxyl number (OH) is a measure of the active hydrogen group content (such as hydroxyl group content) per gram of polyol. The hydroxyl number is measured by titrating a known mass of polyol against potassium hydroxide (KOH) and is expressed in mg KOH / g. The lower the hydroxyl number, the lower the active hydrogen content and the hydroxyl content, indicating that the molecular weight of the polyol is higher. The OH equivalent is the number of grams of a given product containing one equivalent of hydroxyl groups (OH), equivalent = 56100 / OH. Molecular weight is determined by multiplying the equivalent weight by the polyol functionality.

  A composition comprising a) a plurality of polyester macromers, and b) a composition comprising a polymer comprising pendant Michael addition reaction donor groups, as disclosed herein, the desired properties of a coating prepared therefrom And each may contain sufficient amounts. Such compositions may also contain compositions comprising a plurality of polyester macromers in an amount of about 40 weight percent or more, about 50 weight percent or more, or about 60 weight percent or more based on the total weight of the coating composition. Good. Such compositions may also contain compositions containing multiple polyester macromers in an amount of about 90 weight percent or less, about 70 weight percent or less, or about 50 weight percent or less based on the total weight of the coating composition. Good. Such compositions contain a polymer containing pendant Michael addition reaction donor groups in an amount of about 10 weight percent or more, about 30 weight percent or more, or about 40 weight percent or more based on the total weight of the coating composition. May be Such compositions contain a polymer containing pendant Michael addition reaction donor groups in an amount of about 60 weight percent or less, about 50 weight percent or less, or about 40 weight percent or less based on the total weight of the coating composition. May be

  The composition comprising a) a plurality of polyester macromers and b) the composition comprising a polymer comprising pendant Michael addition reaction donors may further comprise c) one or more polar aprotic solvents. The polar aprotic solvent may be volatilized away from the components once the coating is applied to the substrate. Any polar aprotic solvent that volatilizes away from the other components once applied to the surface of the substrate may be utilized herein. The polar aprotic solvent may exhibit a boiling point of about 100 ° C. or more, about 110 ° C. or more, or about 130 ° C. or more. The polar aprotic solvent may exhibit a boiling point of about 200 ° C. or less, about 190 ° C. or less, or about 170 ° C. or less. The polar aprotic solvent may be an alkylene glycol ether, an acetate modified alkylene glycol ether, a ketone, or a mixture of any of these solvents, and the like. The polar aprotic solvent is sufficient to adjust the viscosity of the composition to facilitate application of the composition to a substrate, and provide proper wet out of the composition on the surface to be coated It may be present in an amount sufficient to enable it. Such compositions may contain solvent in an amount of about 0 weight percent or more, about 1 weight percent or more, or about 10 weight percent or more based on the total weight of the coating composition. Such compositions may contain the solvent in an amount of about 30 weight percent or less, about 20 weight percent or less, or about 15 weight percent or less based on the total weight of the coating composition.

式中、Ｆは、出現する度に別々に、直接結合、アニオン重合または遊離基重合によって不飽和基と重合する化合物の残基であり得る。Ｆは、出現する度に別々に、直接結合、１，１−ジエステル−１−アルケンまたは多官能性モノマーの残基であり得る。点線は、重合したマクロマーの骨格を指す。ポリエステルマクロマーを含有する架橋組成物の架橋密度は、組成物の所望の特性をもたらすような任意の密度であり得る。ポリエステルマクロマーの一部分またはすべてが、ポリマーから懸垂するマイケル付加反応供与体の、ポリエステルマクロマーの１アルケン基へのマイケル付加反応によって架橋されてもよい。ポリオールから懸垂するマイケル付加反応供与体の、ポリエステルマクロマーの１アルケンへのマイケル付加反応による架橋は、式１８に相当し得る：

式中、Ｘは、マイケル付加反応供与体の残基であり；Ｒ^ｘは、マイケル付加反応供与体の残基が結合しているポリマーまたは基材である。Ｘは、出現する度に独立に、Ｏ、ＮＲ^ｙ、またはＳであってもよい。Ｒ^ｘは、出現する度に独立に、アクリルポリオール、アミン変性アクリルポリオール、ポリカーボネートポリオール、変性アクリルコポリマーポリオール、ポリエーテルアミン、ポリエステルポリオール、ポリエーテルポリオール、もしくはシロキサンポリオールを含むポリマー、または基材であってもよい。Ｒ^ｙは、上文に記載した通りのＨまたはヒドロカルビル基であってもよい。ポリエステルマクロマーは、１，１−アルケン基を通して、及び１アルケン基への、ポリマーから懸垂したマイケル付加反応供与体のマイケル付加反応によって架橋されてもよい。代替的に、ポリエステルマクロマーは、１，１−二置換アルケン及び／または多官能性モノマーを含めた化合物の不飽和基によって、当業者に周知の通りの遊離基またはアニオン付加プロセスを介して架橋されてもよい。 The polyester macromer compositions disclosed herein can be used to prepare coatings. Such structures may be cured and / or crosslinked. The crosslinked composition may be crosslinked through the alkene group pendant from the macromer chain. The bridge may be a direct bond between the alkene groups of nearby macromer chains. Macromer chains may be included in the prepolymer or polymer chain. The macromer chains may be crosslinked through any compound having unsaturation that polymerizes by anionic or free radical polymerization. The polyester macromer chain may be crosslinked through the 1,1-diester alkene, the crosslinking comprising the residues of the 1,1-diester alkene. The polyester macromer chains may be crosslinked through multifunctional monomers, the crosslinking comprising residues of multifunctional monomers. Crosslinking between chains can be illustrated by Formula 16:

Where F may be the residue of a compound which polymerizes with the unsaturated group by direct bonding, anionic polymerization or free radical polymerization separately on each occurrence. F may be a residue of a direct bond, 1,1-diester-1-alkene or multifunctional monomer separately on each occurrence. The dotted line refers to the backbone of the polymerized macromer. The crosslink density of the crosslinkable composition containing the polyester macromer may be any density that provides the desired properties of the composition. A part or all of the polyester macromer may be crosslinked by the Michael addition reaction of a pendant Michael addition reaction donor from the polymer to one alkene group of the polyester macromer. Crosslinking by Michael addition reaction of a polyester macromer to an alkene of a polyester with a pendant Michael addition reaction donor from a polyol may correspond to Formula 18:

Where X is the residue of the Michael addition reaction donor; R ^x is the polymer or substrate to which the residue of the Michael addition reaction donor is attached. X may be O, NR ^y or S independently at each occurrence. R ^x is, independently of each occurrence, a polymer or substrate comprising an acrylic polyol, an amine modified acrylic polyol, a polycarbonate polyol, a modified acrylic copolymer polyol, a polyether amine, a polyester polyol, a polyether polyol or a siloxane polyol May be R ^y may be H or a hydrocarbyl group as described above. The polyester macromer may be crosslinked by a Michael addition reaction of a pendant Michael addition reaction donor from the polymer through the 1,1-alkene group and to one alkene group. Alternatively, the polyester macromer is cross-linked via free radical or anionic addition processes as is well known to those skilled in the art, by unsaturated groups of compounds including 1,1-disubstituted alkenes and / or polyfunctional monomers. May be

  The polyester macromers and compositions containing them can be polymerized upon exposure to a basic initiator. When applied to the surface of a basic substrate, the polyester macromer cures via anionic polymerization. The polyester macromer and the composition containing the polyester macromer can be polymerized when contacted with a composition containing a basic material as a polymerization activator. Polymerization activators and methods of delivering the polymerization activators are disclosed in Malofsky, US 9,181,365, which is incorporated herein by reference in its entirety for all purposes. The polymerization activator may be at least one of a base, a base improver, a base generator, or a base precursor. The polymerization activator may be a strong base (pH greater than 9), a medium strong base (pH 8 to 9), or a (weakly basic) weak base (pH greater than 7 to 8), or a combination thereof It may contain the selected basic material. The polymerization activator may comprise a basic material selected from organic materials, inorganic materials, or organometallic materials, or combinations thereof. The polymerization activators are sodium acetate; potassium acetate; salts of acids of sodium, potassium, lithium, copper and cobalt; tetrabutylammonium fluoride, chloride and hydroxide; primary, secondary or tertiary Amides; salts of acids bound to polymers; benzoates; 2,4-pentanedionates; sorbates; propionates; secondary fatty amines; piperidine, piperazine, N- Methyl piperazine, dibutylamine, morpholine, diethylamine, pyridine, triethylamine, tripropylamine, triethylenediamine, N, N-dimethylpiperazine, butylamine, pentylamine, hexylamine, heptylamine, nonylamine, decylamine; amine and organic monocarboxylic acid Salts of piperidine Tates; metal salts of lower monocarboxylic acids; copper (II) acetate, cupric acetate monohydrate, potassium acetate, zinc acetate, zinc chloroacetate, magnesium chloroacetate, magnesium acetate; salts of acid-containing polymers; polyacrylics It may be at least one member selected from a salt of an acid copolymer or a dye having basicity. In certain embodiments, the polymerization activator is encapsulated in a wax or prepared in inactive engagement with the polymerizable composition by chemical inactivation.

  Disclosed is a polymerizable system comprising a polymerizable composition comprising one or more polyester macromers and one or more polymers having pendant Michael addition reaction donating groups; and a polymerizable composition physically A polymerizable system comprising a separated polymerization activator, wherein the polymerization activator can initiate polymerization upon contact with the polymerizable composition without substantial mixing. The polymerization activator may be physically separated from the polymerizable composition, and physical separation is achieved by housing the activator and the polymerizable composition in separate locations within the applicator means. The applicator means may be an aerosol spray device. Physical separation may be achieved by first applying a polymerization activator to at least a portion of the substrate and subsequently applying a polymerizable composition to the portion of the substrate. In still other embodiments, physical separation may be achieved by providing a polymerization activator in or on at least a portion of the substrate. The polymerization activator may be physically separated from the polymerizable composition, wherein the polymerization activator is in an inactive state, wherein the polymerizable system switches the polymerization activator from the inactive state to the active state. It further comprises a converting agent that can be converted. The basic polymerization initiator may be enclosed in a composition that can be subjected to the process of releasing the initiator. The encapsulated initiator particles comprise an initiator matrix. The initiator matrix comprises a first cured composition formed from one or more 1,1-disubstituted alkene compounds, and one or more polymerization initiators substantially encapsulated in the first cured composition. Including. Representative compositions are disclosed in US 9,334,430, which is incorporated herein by reference in its entirety for all purposes.

  Disclosed are, in a first part, one or more polyester macromer as disclosed herein and one or more polymer having a pendant Michael addition reaction donor group, and in a second part, a polyester macromer A composition containing one or more compounds having sufficient basicity to initiate anionic polymerization of one or one or more compounds catalyzing a Michael addition reaction, the combination of the two parts curing the polyester macromer Composition. Any of the basic materials disclosed herein may be used. The one or more compounds having basicity may be one or more amines or polyamines. The one or more basic compounds may be one or more polyalkyleneimines, such as polyethyleneimine. Compounds that catalyze the Michael addition reaction include acids and bases. The compound that catalyzes the Michael addition reaction is an amount of at least about 0.01 weight percent, at least about 0.05 weight percent, at least about 0.1 weight percent, or at least about 0.3 weight percent based on the weight of the formulation. May exist. The compound that catalyzes the Michael addition reaction may be present in an amount of about 1 weight percent or less, about 0.5 weight percent or less, or about 0.2 weight percent or less based on the weight of the formulation.

  The polyester macromers and compositions containing them may be used to prepare polyester based structures comprising one or more polymers having pendant Michael addition reaction donating groups, such as coatings on substrates. Disclosed are coatings comprising a residue of a polyester macromer, or a polyester macromer and one or more polymers having pendant Michael addition reaction donating groups. Coatings containing residues of a polyester macromer, or a polyester macromer and one or more polymers having pendant Michael addition reaction donating groups can be disposed on one or more surfaces of the substrate or a portion thereof. The coating may be cured and / or crosslinked. The film or coating may have a thickness of about 0.01 micrometer or more, about 0.04 micrometer or more, about 0.1 micrometer or more, or about 1 micrometer or more. The coating may be cured and / or crosslinked. The coating is about 160 micrometers or less, about 140 micrometers or less, about 100 micrometers or less, about 60 micrometers or less, about 40 micrometers or less, about 10 micrometers or less, about 2 micrometers or less, or about 1 micrometer It may have the following thickness. Disclosed is an article comprising a substrate having a coating applied to one or more surfaces, wherein the coating comprises one or more polyester macromers, or one or more polyester macromers and a pendant Michael addition reaction. An article comprising a composition comprising one or more polymers having a donor group.

  Disclosed is an article comprising a substrate, wherein the substrate comprises a colored basecoat on the substrate and one having the polyester macromer disclosed herein and a pendant Michael addition reaction donor group. A coating comprising the above polymer is disposed on a base coat. The basecoat may have sufficient basicity to cure and / or crosslink the polyester macromer and one or more polymers having pendant Michael addition reaction donating groups. Coatings containing a polyester macromer and one or more polymers with pendant Michael addition reaction donating groups may be clear or function as a clear coat. The disclosed coatings may contain any additional components utilized in the coating, such as, for example, dyes, adhesion promoters, flame retardants, and components disclosed herein. The coatings disclosed herein may contain a dye and may function as a sole coat of a basecoat, with a clearcoat disposed on such a basecoat. Disclosed is a system comprising a basecoat and a clearcoat comprising the composition disclosed herein, wherein the composition comprises one or more polyester macromer and one or more pendant Michael addition reaction donor groups. Containing the polymer of

  The polyester macromers or compositions containing them may be added to any composition containing components for preparing the polyester to introduce alkene units into the backbone. The composition comprises diols and diesters known to those skilled in the art of preparing polyesters. Polyester macromers or compositions containing them may be added to blends containing polyester to add alkene functionality. Compositions containing polyester macromers or compositions containing them may be crosslinked as disclosed herein.

  Polyester macromers can be prepared from polyols, diols, and diesters. The diesters include one or more 1,1-diester-1-alkenes and may include dihydrocarbyl dicarboxylates. The final structure of the polyester macromer can be determined by the proportions of reactants disclosed above and the synthetic order of the intermediates. Intermediates and polyester macromers can be prepared by transesterification. Polyols and diols having more than two hydroxyl groups function to initiate polyester macromer chains. The diol also functions to react with the diester to form a macromer chain. 1,1-Diester-1-alkenes react with polyols and diols to form macromer chains and introduce pendant alkene groups into the macromer chains. Dihydrocarbyl dicarboxylates react with polyols and diols to form macromer chains and function to spread pendant alkene groups on the macromer chains. Polyester macromers can be prepared by contacting polyols, diols and diesters and subjecting them to transesterification conditions. The resulting polyester macromer may have a somewhat random and uncontrolled structure. As it is possible to control the final structure using intermediates, it may be desirable to prepare intermediates and to prepare polyester macromers using the intermediates.

  The multifunctional monomer is a transesterification catalyst of an equivalent excess of one or more polyols to one or more 1,1-diester 1-alkenes under conditions such that one or more multifunctional monomers are formed. It can be prepared by contacting in the presence, said multifunctional monomers contain one or more polyols, 1, 1-diester 1-alkenes of which two or more of their hydroxyl groups are one or more Is replaced by the residue of The equivalent ratio of the one or more 1,1-diester 1-alkenes to the one or more polyols may be about 2: 1 or more or about 4: 1 or more. The equivalent ratio of the one or more 1,1-diester 1-alkenes to the one or more polyols may be about 5: 1 or less or about 3: 1 or less. Multifunctional monomers may be used to control the number of chains in the polyester macromer and / or to form the polyester macromer chains in a controlled manner. Polyol-terminated dihydrocarbyl dicarboxylates are prepared under conditions such that one or more dihydrocarbyl dicarboxylates having the residue of the polyol attached to each of the carbonyl groups are prepared The rate can be prepared by contacting an excess amount of one or more polyols in the presence of a transesterification catalyst. The equivalent ratio of one or more diols to one or more dihydrocarbyl dicarboxylates may be about 2: 1 or more. The equivalent ratio of one or more diols to one or more dihydrocarbyl dicarboxylates may be about 4: 1 or less or about 3: 1 or less.

  Disclosed are one or more polyfunctionals containing one or more polyols, wherein two or more of their hydroxyl groups are replaced by the residue of one or more 1,1-diester 1-alkenes Contacting one or more polyols with an equivalent excess of one or more 1,1-diester 1-alkenes in the presence of a transesterification catalyst under conditions such that a monomeric monomer is formed; and Polyester macromer comprising one or more chains of residues of one or more diols and one or more 1,1-diester-1-alkenes, one or more diols and one or more , 1-diester-1 alkene residues alternately along the chain, at least one end comprising one residue of 1,1-diester-1 alkene, one or more ends being one More than diol Under conditions such that one or more polyester macromers are prepared, which may contain groups, the multifunctional monomer is added in an amount of 1 provided that the polyol is a diol in the presence of a transesterification catalyst. Contacting with one or more polyols, or contacting with one or more second polyols that are diols. One comprising a multifunctional monomer and an additional amount of one or more polyols or one or more second polyols, one or more dihydrocarbyl dicarboxylates with the residue of the polyol attached to each of the carbonyl groups The above compounds are contacted in such a way that one or more polyester macromers are prepared, wherein at least a portion of the polyester macromers contain one or more residues of dihydrocarbyl dicarboxylate in their backbone . The one or more compounds comprising one or more dihydrocarbyl dicarboxylates having the residue of a polyol attached to each of the carbonyl groups is one or more compounds having the residue of the polyol attached to each of the carbonyl groups The hydrocarbyl dicarboxylate is prepared by contacting one or more dihydrocarbyl dicarboxylates with an excess of one or more polyols in the presence of a transesterification catalyst under conditions such that the hydrocarbyl dicarboxylate is prepared.

  Disclosed is one or more containing one or more chains of residues of one or more diols, one or more dihydrocarbyl dicarboxylates, and one or more 1,1-diester-1-alkenes Of one or more diols, one or more 1,1-diester 1-alkenes, and one or more dihydrocarbyl dicarboxylates in the presence of a transesterification catalyst under conditions such that a polyester macromer of Wherein each residue is arranged in a random fashion along the chain, at least one end comprising one residue of a 1,1-diester-1 alkene, one It is a method, wherein the ends above may comprise residues of one or more diols and / or one or more dihydrocarbyl dicarboxylates.

  Disclosed are one or more polyfunctionals containing one or more polyols, wherein two or more of their hydroxyl groups are replaced by the residue of one or more 1,1-diester 1-alkenes Contacting one or more polyols with an equivalent excess of one or more 1,1-diester 1-alkenes in the presence of a transesterification catalyst under conditions such that a monomeric monomer is formed; and Polyester macromer comprising one or more chains of residues of one or more diols, one or more dihydrocarbyl dicarboxylates, and one or more 1,1-diester-1-alkenes, Each residue is arranged in a random fashion along the chain, at least one end comprising one residue of the 1,1-diester-1 alkene, and one or more ends represent one or more di- And / or one or more of the multifunctional monomers, under conditions under which one or more polyester macromers are prepared, which may contain residues of one or more dihydrocarbyl dicarboxylates. Contacting the diol, one or more 1,1-diester 1-alkenes, and one or more dihydrocarbyl dicarboxylates in the presence of a transesterification catalyst.

  Disclosed are one or more dihydrocarbyl dicarboxylates having residues of one or more polyols, one or more 1,1-diester-1-alkenes, and a polyol attached to each of the carbonyl groups. Containing one or more chains of residues of the compound, at least one end comprising one residue of 1,1-diester-1 alkene, one or more ends comprising one or more diols and / or Or with one or more 1,1-diester 1-alkene residues under conditions such that one or more polyester macromers are prepared, which may contain one or more residues of dihydrocarbyl dicarboxylate One or more polyfunctional monomers containing one or more polyols having a substituted hydroxyl group; the residue of the polyol bound to each of the carbonyl groups A method comprising causing or one or more polyols are contacted in the presence of a transesterification catalyst; one or more compounds containing a dihydrocarbyl bilge carboxylates.

  In the disclosed method, the one or more polyols or the second polyol may be a diol. The one or more dihydrocarbyl dicarboxylates may be aromatic dicarboxylates, aliphatic dicarboxylates, alicyclic dicarboxylates or different hydrocarbyl groups selected from aromatic, aliphatic and alicyclic groups And one or more of dihydrocarbyl dicarboxylates. Oxygen from hydroxyl groups on diols and polyols is attached to aliphatic carbon atoms.

  Transesterification is an equilibrium process, typically under conditions that remove by-products formed during exchange (meaning the product formed by the hydrocarbyl moiety leaving the ester to be transesterified) To be executed. The hydrocarbyl moiety leaving the ester group of the ester compound may be smaller than the hydrocarbyl moiety replacing them, and the by-products may be more volatile than the ester compound to be transesterified. The smaller by-products are generally more volatile than the ester compounds to be transesterified, whereby removal of the by-products is facilitated due to their volatility. The disclosed process can be used at any process conditions that remove by-products formed from leaving hydrocarbyl moieties. Representative process conditions or steps that may be used to remove by-products formed from leaving hydrocarbyl moieties may include one or more of distillation, membrane transport, inert gas purge, and the like.

  The transesterification reaction may be carried out in the presence of a catalyst such as, for example, an acid, an ester of such an acid, or an enzyme. The transesterification catalyst may be an enzyme. The transesterification catalyst may be a lipase enzyme. A transesterification process utilizing enzymes is disclosed in US2014 / 0329980 (incorporated herein by reference in its entirety for all purposes).

  The catalyst may be an acid or an ester thereof. A transesterification process using an acid or an ester is disclosed in commonly owned patent US 9,416,091 which is incorporated herein by reference in its entirety for all purposes. Any acid or ester thereof may be used which catalyzes transesterification while minimizing side reactions. In some embodiments, the acid or acid utilized to form the ester is an acid having a pKa in a polar aprotic solvent such as acetonitrile or dioxane as disclosed below. The pKa may be selected to minimize the concentration of catalyst in the side reactions and reaction mixture while efficiently catalyzing the transesterification reaction. The acid used may have a pKa of about -5 or more, about -3 or more, or about 1.0 or more. The acid used may have a pKa of about 14 or less, about 11 or less, or about 9 or less. The acid may be a Bronsted acid having a pKa as disclosed. The catalyst may be a super acid or an ester thereof. By superacid is meant an acid having an acid strength greater than that of 100 percent sulfuric acid. The ester, when acid catalyzed, refers to a compound in which the hydrogen on the acid is replaced by a hydrocarbyl group, such as an alkyl group. A super acid is an acid having a pKa of less than 100 percent sulfuric acid, ie, a pKa of less than 8, less than about 5, or less than about 2, which is a greater strength than that of 100 percent sulfuric acid. Acid strength measurements were published on the web on Dec. 17, 2010, Kutt et al. Based on "Equilibrium Acids of Super Acids," Journal of Organic Chemistry Vol 76 pages 391 to 395, 2011, which is incorporated herein by reference. Representative super acids include trifluoromethane sulfonic acid (triflic acid), sulfated tin oxide, triflated tin oxide, sulfated zirconia, triflated zirconia, and triflated HZSM-5. Representative super acids are triflic acid and fluorosulfonic acid.

  Representative acid catalysts include triflic acid, fluorosulfonic acid, and sulfuric acid. In the case of a reaction requiring mono substitution (only one hydroxyl group on the alcohol or one ester group on the second ester is replaced by transesterification), weaker acids with a pKa value over sulfuric acid may be desired . Examples of such acids include sulfuric acid or methanesulfonic acid. In the case of a disubstituted reaction (where two hydroxyl groups on the alcohol or two ester groups on the second ester are replaced by transesterification), a stronger acid with a pKa value below sulfuric acid may be desired. Examples of such acids include sulfuric acid, fluorosulfonic acid and triflic acid. For reactions requiring multiple substitution (three or more hydroxyl groups on alcohol and three or more ester groups on another ester compound), the choice of acid catalyst may be similar to that of the disubstituted reaction, but the reaction It may be necessary to increase the time. As esters of acids useful as catalysts, alkyl triflates can be mentioned.

  The catalyst can be mixed with the reactants or supported on a substrate such as a membrane, or an inert support such as a porous support structure (the catalyst can be heterogeneous). Unsupported catalysts are usually referred to as homogeneous. The catalyst can be used at any concentration that catalyzes the transesterification reaction. The amount of catalyst utilized for the reaction depends on the type of catalyst selected. The concentration of the homogeneous catalyst is about 1 molar equivalent or less, about 0.1 molar equivalent or less, about 0.05 molar equivalent or less, about 0.005 molar equivalent or less per equivalent of the ester compound to be transesterified. The concentration of the catalyst is about 0.001 molar equivalent or more, or about 0.0015 molar equivalent or more per equivalent of ester compound to be transesterified. Higher concentrations of catalyst may be utilized than those listed. Malofsky et al. As disclosed in US Pat. No. 8,609,885, 8,884,051 and WO 2013/059473, the presence of an acid in the recovered 1,1-disubstituted alkene compound causes problems with the use of the compound It is desirable that the concentration of acid in the product be low when used. If high levels of acid are included in the final product, additional purification or removal steps may be required. The amounts listed balance the need for efficient catalysis with the need for low acid concentrations in the product used. In embodiments where the catalyst is selected from sulfuric acid or acids having a lower pKa value than sulfuric acid, the concentration of such catalyst in the reaction mixture is preferably at the upper end of the range recited herein. The choice of polyol and / or diester compound and the relative number of moles of polyol and diester will affect the product of the process.

  When the reactants are liquid under the reaction conditions, it is desirable to contact the reactants and the catalyst in undiluted form (ie, without solvent or dispersant). If the use of a solvent is desired, a solvent that does not react with the reactants or catalyst is desirable. Another consideration in the choice of solvent is the boiling point of the solvent chosen. It is desirable for the solvent to have a boiling point of about 15 ° C. or more or about 20 ° C. or more above the temperature at which the reaction is carried out. Aprotic solvents may be used, and long chain alkanes having a boiling point above the reaction temperature described herein may be used. Typical solvents are decane or dodecane. The reactants are contacted at any temperature at which transesterification proceeds. Preferably, the reactants are contacted at a temperature of about 80 ° C. or more, or about 100 ° C. or more. The reactants may be contacted at a temperature of about 160 ° C. or less, 140 ° C. or less, or about 130 ° C. or less. The reactants are contacted for a sufficient time to prepare the desired transesterification product. The process is carried out to prepare the desired product by substantially complete reaction of the starting compound, a first ester compound, such as a 1,1-disubstituted alkene compound, with an alcohol or a second ester compound. It is preferable to do. Preferably, the reactants are contacted for about one hour or more. The reactants may be contacted for up to 4 hours or up to 2 hours.

  It is desirable to carry out the process under conditions in which the contact of the diester with the polyol is enhanced so as to allow replacement of the initial hydrocarbyl moiety on the ester group of the diester. Some form of agitation is desirable to enhance this contact. As a typical stirring method, use of a stirrer, sparging with inert gas and the like can be mentioned. Vigorous stirring and / or vigorous sparging with nitrogen may be used. Transesterification is considered to be an equilibrium reaction. It is recommended to carry out the process under conditions which drive the reaction in the direction of the desired product. Representative ways of achieving this include adding one reactant in excess, removing the alcohol formed by the leaving hydrocarbyl moiety, and the like. If the compound formed from the leaving hydrocarbyl moiety is volatile, it is possible to distill off the leaving alcohol through the use of reduced pressure while not distilling off the other reactants and products Conditions can be used for removal.

  The catalyst may be an enzyme. Transesterification conditions include room temperature and atmospheric pressure; high temperature and pressure; room temperature and reduced pressure; high temperature and reduced pressure; or any combination thereof. The transesterification step may be performed at a temperature of about 20 ° C. or more, about 35 ° C. or more, or about 40 ° C. or more. The transesterification step may be performed at a temperature of about 85 ° C. or less or about 70 ° C. or less.

  Transesterification is described in Malofsky et al. , The presence of free radical stabilizers and anionic polymerization inhibitors as described in US 8, 609, 885, 8, 884, 051, and WO 2013/059473 (related parts are incorporated herein by reference) It may be performed below. It is desirable to include an acid that inhibits polymerization but does not significantly participate in transesterification catalysis in order to prevent formation of the polymer product. The acid used to inhibit polymerization can have a pKa less than 100 percent sulfuric acid. According to certain embodiments, the inclusion of stabilizers in compositions containing transesterification products can increase and improve shelf life and prevent spontaneous polymerization. One or more anionic polymerization stabilizers and / or free radical stabilizers may be added to the composition. Anionic polymerization stabilizers are generally electrophilic compounds that capture nucleophiles from the composition or growing polymer chain. An anionic polymerization stabilizer can be used to terminate the additional elongation of the polymer chain. Representative anionic polymerization stabilizers are acids, and representative acids are carboxylic acids, sulfonic acids, phosphoric acids and the like. Representative stabilizers include liquid phase stabilizers (eg, methanesulfonic acid (“MSA”)) and gas phase stabilizers (eg, trifluoroacetic acid (“TFA”)). It may be desirable to inhibit polymerization using a relatively weak acid. Generally, such weak acids exhibit a pKa of about -1.5 or less in acetonitrile. Representative acids used to inhibit anionic polymerization are alkyl substituted aryl sulfonic acids such as dodecyl benzene sulfonic acid, p-toluene sulfonic acid and the like. As the catalyst in the disclosed method is an acid, a second anionic polymerization inhibitor may be unnecessary in the practice of the method disclosed herein. In the practice of the methods disclosed herein, it is desirable to include free radical stabilizers or polymerization inhibitors. Concentrations of stabilizers or polymerization inhibitors useful in the method are disclosed below.

  The free radical stabilizers preferably comprise phenolic compounds (e.g. 4-methoxyphenol, monomethyl ether of hydroquinone ("MeHQ"), butylhydroxytoluene ("BHT")). Stabilizer packages for 1,1-disubstituted alkenes are disclosed in US Pat. Nos. 8,609,885 and 8,884,051, each of which is incorporated by reference. Additional free radical polymerization inhibitors are disclosed in US Pat. No. 6,458,956, which is incorporated herein by reference. In general, only a minimal amount of stabilizer is required, and in certain embodiments, it may contain less than or equal to about 5000 parts per million ("ppm"). In certain embodiments, a blend of stabilizers can be included, for example, a blend of an anionic stabilizer (MSA) and a free radical stabilizer (MeHQ).

  The one or more anionic polymerization stabilizers are present in an amount sufficient to prevent premature polymerization. The anionic polymerization stabilizer may be present in an amount of about 1 ppm or more, about 5 ppm by weight or more, or about 10 ppm by weight or more based on the weight of the first ester compound (1,1-disubstituted alkene). The anionic polymerization stabilizer may be present in an amount of about 500 ppm by weight or less, about 250 ppm by weight or less, or about 100 ppm by weight or less based on the weight of the ester compound (1,1-disubstituted alkene). The one or more free radical stabilizers are present in an amount sufficient to prevent premature polymerization. The free radical polymerization stabilizer may be present in an amount of about 10 ppm or more, about 100 ppm by weight or more, or about 1000 ppm by weight or more based on the weight of the ester compound (1,1-disubstituted alkene). The free radical polymerization stabilizer is present in an amount up to about 10,000 ppm by weight, up to about 8000 ppm by weight, or up to about 5000 ppm by weight based on the weight of the ester compound (1,1-disubstituted alkene). Good.

  Disclosed is contacting a composition comprising at least one polyester macromer and at least one polymer having a pendant Michael addition reaction donor with a surface of a substrate that is at least weakly basic, and Forming on the surface of the substrate a coating comprising a composition comprising one or more polyester macromers and one or more polymers having pendant Michael addition reaction donating groups. The substrate is composed of a material that is basic. Prior to applying the composition containing one or more polyester macromers, the composition containing the basic compound may be applied to the surface of the substrate. Compositions containing basic compounds may include any of the compounds disclosed herein as anionic polymerization inhibitors useful for 1,1-diester-1-alkenes. Representative basic compounds include amines, polyamines, basic dyes, or carboxylates. The composition containing the basic compound may contain a polyalkyleneimine. The method exposes a substrate having a composition comprising one or more polyester macromers and one or more polymers having pendant Michael addition reaction donors to a temperature of about 20 ° C. or more, or about 50 ° C. or more. May further include the following. The method exposes a substrate having a composition comprising one or more polyester macromers and one or more polymers having pendant Michael addition reaction donors to a temperature of about 150 ° C. or less or about 120 ° C. or less May further include the following. The time of such exposure may be about 10 minutes or more or about 20 minutes or more. The time of such exposure may be 120 minutes or less, about 60 minutes or less, or about 30 minutes or less. The exposure is such that a coating comprising one or more polyester macromers and one or more polymers having pendant Michael addition reaction donors disposed on the surface of the substrate is cured and / or crosslinked. Is executed by

  The polyester macromer containing the coating or film may be cured and / or crosslinked when exposed to certain conditions. When the coatings or coatings are exposed to relatively strong bases and / or high temperatures, they are simultaneously cured and crosslinked. If they are exposed to weakly basic materials at relatively low temperatures, less than about 50 ° C. or less than about 40 ° C., they may not be fully cured or crosslinked. Such coatings or films may be cured by exposure to elevated temperatures to cure as disclosed herein.

  Coatings prepared from one or more polyester macromers and one or more polymers having pendant Michael addition reaction donor groups can exhibit one or more of the following properties listed below. Gloss of 40 GU or more, 50 GU or more, or 60 GU or more at 20 ° according to ASTM D523-08. Pencil hardness of 3H or more, 4H or more, or 5H or more according to ASTM D3363-00. Solvent resistance of about 80 times or more, 100 times or more of friction, or 200 times or more of friction of methyl ethyl ketone according to ASTM D5402-93. 70% or more, 80% or more, or 90% of the mandrel flexibility according to ASTM D522-93; 4B or more and 100% crosshatch adhesion according to ASTM D3359-09. Acid resistance up to 40 ° C, up to 50 ° C, or up to 60 ° C according to GMW 14701. Basic resistance to 40 ° C. or higher, 50 ° C. or higher, or 60 ° C. or higher according to GMW 14701. The coating can withstand exposure to xenon arc UV / moisture according to ASTM D7869 for 500 hours, 1000 hours without loss of gloss or color, and changes in gloss or blistering and corrosion to salt spray tests according to GMW 3286-11 Can withstand for 500 hours without having symptoms of

に相当し、式中、Ｒ^２は前述される通りである；ポリエステルマクロマーを調製するために使用されるポリオールが、分岐状の１つ以上の脂肪族骨格を含んでもよい；ポリエステルマクロマーを調製するために使用される１つ以上のポリオールが、２炭素原子上に少なくとも１つの分岐及び脂環式骨格を有する１つ以上の分岐脂肪族鎖を含んでもよい；１つ以上のポリオールが、ペンタンジオール、ヘキサンジオール、ネオペンチルグリコール、２−メチル−１，３−プロパンジオール、２−ブチル−１，３−プロパンジオール、２−エチル−１，３−プロパンジオール、またはシクロヘキサンジメタノールを含んでもよい；ポリエステルマクロマーが、式３に相当する；ポリエステルマクロマーが、式４に相当する；ポリエステルマクロマーが、式５に相当する；マクロマー中のｄ対ｅの比率が約１：１〜約４：１である、式４または５によるポリエステルマクロマー；各鎖に含有される約１〜約４つのジヒドロカルビルジカルボキシレートを有する、ポリエステルマクロマー；式６に相当するポリエステルマクロマー；ｉ）本明細書に記載する複数のポリエステルマクロマー、ｉｉ）１つ以上のポリオール及び１つ以上の１，１−ジエステル−１−アルケンの残基を含有する１つ以上の多官能性モノマーであって、該多官能性モノマーのポリオールのヒドロキシル基の実質的にすべてが１，１−ジエステル−１−アルケンで置き換えられている多官能性モノマー、及びｉｉｉ）１つ以上の１，１−ジエステル−１−アルケンを含む組成物であって、かかる組成物が、ｉ）約１０〜約９０重量パーセントの複数のポリエステルマクロマー、ｉｉ）約１〜約５０重量パーセントの１つ以上の多官能性モノマー、及びｉｉｉ）約１〜約３０重量パーセントの１つ以上の１，１−ジエステル−１−アルケンを含んでもよく、百分率が、列記した成分の量に基づく、組成物；ポリエステルマクロマーを調製するために使用される１つ以上のポリオールが、ジオールであり得る；ポリエステルマクロマーを調製するために使用される１つ以上の多官能性モノマーが、二官能性モノマーであり得る；ａ）本明細書に開示する通りのポリエステルマクロマー含有組成物、ｂ）揮発性溶媒、ｃ）任意選択により、追加量の１つ以上の１，１−ジエステル−１−アルケン、ｄ）１つ以上の湿潤剤及び均染剤、ｅ）１つ以上のＵＶ安定剤及び／または紫外線吸収剤、ならびにｆ）１つ以上の消泡剤を含む組成物であって、かかる組成物が、ａ）約１０〜約９０重量パーセントの本明細書に開示する通りのポリエステルマクロマー含有組成物、ｂ）約１〜約５０重量パーセントの揮発性溶媒、ｃ）約０〜約４０重量パーセントの１つ以上の１，１−ジエステル−１−アルケン、ｄ）約０．０１〜約２重量パーセントの１つ以上の湿潤剤及び均染剤、ｅ）約０．０１〜約３重量パーセントの１つ以上のＵＶ安定剤及び／または紫外線吸収剤、ならびにｆ）約０．０１〜約２重量パーセントの１つ以上の消泡剤を含んでもよく、百分率が、構成成分ａ、ｂ、ｃ、ｄ、ｅ、及びｆの重量に基づく、組成物；コーティングの形態に硬化される、本明細書に開示する通りの組成物；コーティングが、約１マイクロメートル〜約１００マイクロメートルの厚さを呈する；コーティングが、約２〜１６０ミクロンの厚さを呈する；複数のポリエステルマクロマーを含有する組成物であって、ポリエステルマクロマーの一部分またはすべてが１，１−アルケン基を通して架橋される、組成物；鎖間の架橋が式１７によって図示され得る、組成物；Ｆが、出現する度に別々に、直接結合、１，１−ジエステル−１−アルケンまたは多官能性モノマーの残基であり得る、式１７による組成物；ポリエステルマクロマーの一部分またはすべてが、ポリマーから懸垂するマイケル付加反応供与体の、ポリエステルマクロマーの１アルケン基へのマイケル付加反応によって架橋される、組成物；ポリオールから懸垂するマイケル付加反応供与体の、ポリエステルマクロマーの１アルケン基へのマイケル付加反応による架橋が、式１８に相当する、組成物；Ｘが、出現する度に独立に、Ｏ、ＮＲ^ｙ、またはＳであり；Ｒ^ｘが、出現する度に独立に、アクリルポリオール、アミン変性アクリルポリオール、ポリカーボネートポリオール、変性アクリルコポリマーポリオール、ポリエステルポリオール、ポリエーテルポリオール、もしくはシロキサンポリオールを含むポリマーまたは基材である、式１８による組成物；ポリエステルマクロマーが、１，１−アルケン基を通して、及び／またはポリマーから懸垂するマイケル付加反応供与体の、１アルケン基へのマイケル付加反応によって架橋される；硬化されたコーティングが、以下の特性の１つ以上を呈する：ＡＳＴＭ Ｄ５２３−０８による、２０°、または６０°、または８５°での４０ＧＵ以上の光沢；ＡＳＴＭ Ｄ３３６３−００による３Ｈ以上の鉛筆硬度；ＡＳＴＭ Ｄ５４０２−９３による、メチルエチルケトンの摩擦８０回以上の耐溶剤性；ＡＳＴＭ Ｄ５２２−９３による８０パーセント以上のマンドレル可撓性；ＡＳＴＭ Ｄ３３５９−０９による４Ｂ以上及び１００パーセントのクロスハッチ接着性、ならびにＧＭＷ １４７０１による最大７０℃の耐酸性及び７０℃より高い耐塩基性；ペンダント型マイケル供与基を有するポリマーが、約５０〜約２００のヒドロキシル価を呈する；ならびに、以下の構成成分：色素、充填剤、補強剤、滑り防止添加剤、及び耐摩耗性を改善するための添加剤の１つ以上をさらに含む、本明細書に記載する通りの組成物。 The disclosed article / composition may further comprise any combination of any one or more of the features described herein, including the preferences and examples listed herein, one of the following features: Containing at least one pendant group: pendant type Michael addition reaction donor group includes a functional group containing an active hydrogen atom; pendant type Michael addition reaction donor group includes an amine, hydroxyl, thiol, or a mixture thereof; Michael addition reaction The donor group comprises an amine and / or hydroxyl and the composition comprises one or more chains of alternating residues of one or more diols and one or more diesters, each of the chains being 3 Attached at one end to the oxygen of the residue of a polyol having one or more oxygen atoms; the polyester macromer corresponds to formula 1; when used in several formulas c May be an integer of about 3 to about 6; one or more polymers having a pendant type Michael addition reaction donating group are an acrylic polyol, an amine modified acrylic polyol, a polycarbonate polyol, a modified acrylic copolymer polyol, a polyester polyol, a polyether polyol And one or more of the siloxane polyols; one or more polymers having pendant Michael addition reaction donating groups include one or more acrylic polyols or amine modified acrylic polyols; a) about 40 to about 90 weight percent And one or more polyester macromer, and about 10 to 60 percent by weight of one or more polymers having pendant Michael addition reaction donating groups, optionally including a solvent, in an amount of the composition Based on weight, ahead A composition according to any one of the claims; the solvent may comprise one or more polar aprotic solvents; one or more alkylenes, the solvents having a boiling point of about 80 ° C to about 200 ° C. The glycol ether, acetate modified alkylene glycol ether, or ketone may be included; the solvent is present in an amount of about 5 to about 40 weight percent, the amount being based on the weight of the composition; the polyester macromer is one or more diols And one chain of residues of one or more diesters; polyester macromer may correspond to Formula 2; polyester macromer may exhibit a number average molecular weight of about 400 to about 3000 Oxygen from hydroxyl group on diol and polyol of polyester macromer may be bonded to aliphatic carbon atom; One or more chains of lumacromers may comprise one or more residues of dihydrocarbyl dicarboxylate; an aromatic having one or more dihydrocarbyl dicarboxylates having 8 to 14 carbon atoms in the backbone Group dicarboxylates, aliphatic dicarboxylates having 1 to 12 carbon atoms in the backbone, and one or more alicyclic dicarboxylates having 8 to 12 carbon atoms in the backbone One or more dihydrocarbyl dicarboxylates, one or more malonates, terephthalates, phthalates, isophthalates, naphthalene-2,6-dicarboxylates, 1,3-phenylenedioxydiacetates, cyclohexane dicarboxylates; Cyclohexane diacetate, diphenyl-4,4'-dicarboxylate, succinate , Glutarate, adipate, azelate, sebacate, or mixtures thereof; one or more dihydrocarbyl dicarboxylates including one or more malonates, isophthalates, terephthalates, or sebacates; preparing polyester macromers The polyol used for the formula corresponds to formula 9, the 1,1-diester-1-alkenes correspond to formula 7, and one or more dihydrocarbyl dicarboxylates correspond to formula 11; c = 2 , Polyols used to prepare polyester macromers have the formula

Where R ² is as described above; the polyol used to prepare the polyester macromer may comprise one or more branched aliphatic backbones; preparing the polyester macromer One or more of the polyols used for may also contain one or more branched aliphatic chains having at least one branch and an alicyclic backbone on 2 carbon atoms; one or more polyols are pentanediols , Hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-butyl-1,3-propanediol, 2-ethyl-1,3-propanediol, or cyclohexanedimethanol; A polyester macromer corresponds to formula 3; a polyester macromer corresponds to formula 4; a polyester macromer A polyester macromer according to Formula 4 or 5, wherein the ratio of d to e in the macromer is about 1: 1 to about 4: 1; about 1 to about 4 contained in each chain A polyester macromer having a dihydrocarbyl dicarboxylate; a polyester macromer corresponding to Formula 6; i) a plurality of polyester macromers as described herein; ii) one or more polyols and one or more 1,1-diesters- One or more multifunctional monomers containing a residue of 1-alkene, wherein substantially all of the hydroxyl groups of the polyol of the multifunctional monomer are replaced by 1,1-diester-1-alkenes A composition comprising a multifunctional monomer, and iii) one or more 1,1-diester-1-alkenes, such composition comprising i) about 10 About 90 weight percent of a plurality of polyester macromers, ii) about 1 to about 50 weight percent of one or more multifunctional monomers, and iii) about 1 to about 30 weight percent of one or more 1,1-diesters- The composition may comprise 1-alkene, the percentage being based on the amount of the listed components; one or more of the polyols used to prepare the polyester macromer may be a diol; to prepare the polyester macromer One or more of the multifunctional monomers used for the process may be difunctional monomers; a) polyester macromer containing compositions as disclosed herein, b) volatile solvents, c) optionally Additional amounts of one or more 1,1-diester-1-alkenes, d) one or more wetting agents and leveling agents, e) one or more UV stabilizers and Or a UV absorber, and f) a composition comprising one or more antifoaming agents, such a composition comprising a) about 10 to about 90 weight percent of a polyester macromer containing composition as disclosed herein B) about 1 to about 50 percent by weight of a volatile solvent; c) about 0 to about 40 percent by weight of one or more 1,1-diester-1-alkenes; d) about 0.01 to about 2 percent by weight Percent of one or more wetting agents and leveling agents, e) about 0.01 to about 3 weight percent of one or more UV stabilizers and / or UV absorbers, and f) about 0.01 to about 2 weights A composition, which may comprise a percentage of one or more antifoam agents, the percentage being based on the weight of the components a, b, c, d, e and f; Composition as disclosed in; coating The coating exhibits a thickness of about 2 to 160 microns; a composition containing a plurality of polyester macromers, wherein a portion or all of the polyester macromers are Composition crosslinked through 1,1-alkene groups; composition wherein crosslinking between chains may be illustrated by Formula 17; F separately attached directly to each occurrence, 1,1-diester-1- A composition according to Formula 17 which may be a residue of an alkene or a multifunctional monomer; by Michael addition reaction of a portion or all of the polyester macromer with a pendant Michael addition reaction donor from the polymer to one alkene group of the polyester macromer A crosslinked, composition; a Michael addition reaction donor suspended from a polyol, a polyester Crosslinked via Michael addition reaction to 1 alkene group Terumakuroma corresponds to Formula 18, the composition; X is, independently each time appearing, O, NR y or be ^S,; R ^x is, occurrence A composition according to formula 18 which is a polymer or substrate comprising an acrylic polyol, an amine modified acrylic polyol, a polycarbonate polyol, a modified acrylic copolymer polyol, a polyester polyol, a polyether polyol, or a siloxane polyol, independently of the degree; Cross-linked by Michael addition reaction of 1, 1-alkene groups and / or Michael addition reaction agents suspended from polymers onto one alkene group; cured coatings exhibit one or more of the following properties: 2 according to ASTM D523-08 Gloss of 40 GU or more at 60 °, or 60 °, or 85 °; pencil hardness of 3H or more according to ASTM D3363-00; solvent resistance of 80 times or more of methyl ethyl ketone friction according to ASTM D5402-93; 80 according to ASTM D522-93 Percent or more mandrel flexibility; 4B or more according to ASTM D 3359-09 and 100% crosshatch adhesion, and acid resistance up to 70 ° C. and over 70 ° C. according to GMW 14701; with pendant Michael donor groups The polymer exhibits a hydroxyl number of about 50 to about 200; and one or more of the following components: dyes, fillers, reinforcing agents, anti-slip additives, and additives to improve abrasion resistance The composition as described herein further comprising.

  The disclosed method may further comprise any combination of any one or more of the features described herein, including the preferences and examples listed herein, any one of the following features: The substrate comprising at least one or more of a weakly basic, nucleophilic material, and / or containing a plurality of Michael addition reaction donor groups on its surface; pendant Michael addition reaction donation The group comprises a functional group containing an active hydrogen atom; the pendant Michael addition reaction donor group comprises an amine, hydroxyl, thiol, or a mixture thereof; the Michael addition reaction donor group comprises an amine and / or hydroxyl A substrate has a pigmented coating deposited on its surface, said pigmented coating being weakly basic or nucleophilic; one or more polyester macromers A coating comprising the composition having a clear coating formed on the surface of the substrate, the substrate having a composition comprising one or more polyester macromers deposited on the substrate Exposing the surface of the coating or substrate to a temperature of about 20 ° C. to about 150 ° C. for about 10 minutes to about 120 minutes under conditions such that a coating containing one or more polyester macromers is crosslinked; Containing a catalyst for the Michael addition reaction; the surface of the coating or substrate contains an initiator for anionic polymerization.

Exemplary Embodiments of the Invention The following examples are provided to illustrate the invention but are not intended to limit its scope. All parts and percentages are by weight unless otherwise indicated.

  The reaction procedure is as described below. A three-necked 100 mL round bottom flask with a distillation head, thermometer, vacuum adapter, and recovery flask are assembled using high vacuum grade grease with a heating mantle, thermocouple, and magnetic stirrer. The reaction mixture is subjected to stirring, typically in the range of 400-600 rpm. A vacuum is used to remove the subsequently generated by-products from the reaction mixture. The different pressures in each case are shown below with the mixing time. In some cases, nitrogen gas is used instead of vacuum to purge the mixture. If applicable, it will be shown later. In each case, the molar equivalents are relative to the diethyl methylene malonate ("DEMM") monomer used.

The reaction mixture is analyzed using NMR spectroscopy using 300 MHz NMR. Samples are prepared using chloroform-d (CDCl ₃ ) and hexamethyldisiloxane as an internal standard appearing at about 0 ppm. In the case of 1,1-disubstituted alkene compounds with symmetrical substituents (e.g., DEMM), reactive alkene functional groups (i.e., double bonds) appear at about 6.45 ppm. In the case of 1,1-disubstituted alkene compounds with asymmetric substitution, the reactive alkene functional group appears as a doublet at about 6.45 ppm. In most cases, four NMR scans are performed on each sample specimen with a delay of 20 seconds between scans.

GC-MS is used to determine the conversion of the starting material to the desired transesterification product (s) and to detect the presence of any by-products. A helium gas (carrier gas) purge of about 1 mL / min is used to help the ionized sample reach the MS detector. A typical sample injection volume of about 2-5% of the reaction mixture in 1-2 μL of dichloromethane (CH ₂ Cl ₂ ) is used to inject into the GC-MS instrument. The GC-MS profile method is to maintain the oven at 100 ° C. followed by a 15 ° C./min ramp to 250 ° C. Typical run times range from 18 to 23 minutes. The retention time of 1,1-disubstituted alkene compounds is in the range of 4.5 to 17 minutes based on the method described above, which strongly depends on the substituents and the ease of ionization of certain molecules in the GC chamber Do.

  Gel permeation chromatography (GPC) is used to determine the molecular weight of the polyester macromer formed after transesterification. The calibration curve was plotted using a poly (methyl methacrylate) standard (PMMA) covering a range of 500-1080, 000 in number average molecular weight (Mn). The sample was dissolved in THF and filtered before injection. An injection volume of 10 μL was used at 1 ml / min. The column was maintained at 35 ° C. and 75 bar pressure. A differential index detector is used downstream, which is also maintained at 75 bar pressure. The amounts of various species in the composition were calculated based on the percent area of the molecular weight peak on the chromatogram.

Ingredients and Products Pentanediol DEM Diethyl malonate DEMM Diethyl methylene malonate (diethyl 1-methylene-1,1-dicarboxylate)
MeHQ monomethyl ether hydroquinone MSA methanesulfonic acid catalyst CALB lipase enzyme

Test and Test Procedure-Crosshatch Tape Adhesion ASTM D3359-09 tests for coatings prepared according to the present specification for several properties according to the following procedure.
Specular gloss ASTM D523-08
Pencil hardness ASTM D3363-00
MEK abrasion resistance ASTM D5402-93
Mandrel ASTM D522-93
Wear ASTM D4060-95 (corrected for linear tabers)
Humidity GMW 14729
Acid resistant / basic GMW 14701
Weather resistance (UV + moisture) SAE J2020
Salt spray GMW 3286-11 Neutral salt spray

EXAMPLE 1 Preparation of a Bifunctional Monomer from Pentanediol and DEMM In a round bottom flask, DEMM (172 g, 1 mol), pentanediol (26 g, 0.25 mol), and 5 weight percent CALB lipase enzyme based on DEMM. Add (8.6 g) (purchased from CLEA). The round bottom flask is placed on a rotary evaporator preheated to 45 ° C. and a pressure of 150 mm Hg is applied. After 1 hour, check the reaction completion by GCMS and HNMR. The reaction is complete if pentanediol is consumed. The product mixture is an approximately 65/35 mixture of difunctional monomer and DEMM according to GCMS analysis. The reaction mixture is filtered to remove the enzyme. The reaction mixture formed is placed in a three-necked round-bottomed flask equipped with a mechanical stirrer, thermometer and condenser. The reaction mixture is distilled at 65 ° C. and a pressure of <0.800 mm Hg for 2 hours or until the amount of difunctional monomer is greater than 65 weight percent of the solution. A typical product composition is 67% DEMM-pentanediol multifunctional monomer, and 33% DEMM.

Example 2-Pentanediol-terminated diethyl malonate In a round bottom flask, pentanediol (260 g 2.5 mol), DEM (159 g, 1 mol), and 7 weight percent CALB lipase enzyme (18 g) based on pentanediol Put in (purchased from CLEA). The round bottom flask is placed on a rotary evaporator preheated to 45 ° C. and a pressure of 150 mm Hg is applied. After 1 hour, check the reaction completion by GCMS and HNMR. If the DEM is consumed, the reaction is complete. The reaction mixture is filtered to remove the enzyme. In a three-necked round bottom flask equipped with a mechanical stirrer, thermometer, and condenser, place the reaction mixture at 100 ° C. and less than 0.800 mmHg for 2 hours or the amount of pentanediol is the reaction mixture Distill to about 10 weight percent of (as determined by GCMS). A typical product composition is about 90 weight percent pentanediol terminated diethyl malonate, and about 10 weight percent pentanediol.

実施例４−ポリエステルマクロマーの調製
丸底フラスコに、ＤＥＭＭ−ペンタンジオール二官能性モノマー（１４２ｇ、０．４ｍｏｌ）、メチレンマロン酸ジエチル、（７０ｇ、０．４ｍｏｌ）、ペンタンジオール（１０．８ｇ、０．１０ｍｏｌ）、及びＤＥＭＭ−ペンタンジオール二官能性モノマーに基づいて７重量パーセントのＣＡＬＢリパーゼ酵素（１０ｇ）を入れる。この丸底フラスコを、４５℃に予熱したロータリーエバポレーターに１５０ｍｍＨｇの圧力で設置する。１時間後に、ＧＣＭＳによって反応の完了を調べる（ペンタンジオール−二官能性モノマーの消失）。反応混合物をろ過して酵素を除去する。得られた溶液をＧＰＣによって検査する。生成物の組成は、概して以下から構成される：６０〜７５重量パーセントのポリエステルマクロマー、２０〜３０重量パーセントのペンタンジオール−二官能性モノマー、０〜１０重量パーセントのＤＥＭＭ。１００ｐｐｍのＭＥＨＱ及び１０ｐｐｍのＭＳＡを最終生成物に添加する。ＭＳＡは、１重量パーセントのＭＳＡ ＤＥＭＭ溶液から正確に量り取る。反応は、この反応式によって図示される：

EXAMPLE 3 Preparation of a Polyester Macromer In a round bottom flask, DEMM-pentanediol difunctional monomer (142 g, 0.4 mol) and pentanediol end-capped diethyl malonate (27.6 g 0.1 mol), diethyl methylene malonate, Charge (70 g, 0.4 mol), pentanediol (2.7 g, 0.025 mol), and 7 weight percent CALB lipase enzyme (10 g) based on DEMM-pentanediol bifunctional monomer. The round bottom flask is placed on a rotary evaporator preheated to 45 ° C. at a pressure of 150 mm Hg. After 1 hour, check the completion of the reaction by GCMS (pentanediol-disappearance of the difunctional monomer). The reaction mixture is filtered to remove the enzyme. The resulting solution is examined by GPC. The composition of the product is generally comprised of: 60 to 75 weight percent polyester macromer, 20 to 30 weight percent pentanediol-difunctional monomer, 0 to 10 weight percent DEMM. Add 100 ppm MEHQ and 10 ppm MSA to the final product. MSA is accurately weighed from 1 weight percent MSA: DEMM solution. The reaction is illustrated by this reaction:

EXAMPLE 4 Preparation of a Polyester Macromer In a round bottom flask, DEMM-pentanediol difunctional monomer (142 g, 0.4 mol), diethyl methylene malonate (70 g, 0.4 mol), pentane diol (10.8 g, 0 .10 mol) and 7 weight percent of CALB lipase enzyme (10 g) based on DEMM-pentanediol bifunctional monomer. The round bottom flask is placed on a rotary evaporator preheated to 45 ° C. at a pressure of 150 mm Hg. After 1 hour, check the completion of the reaction by GCMS (pentanediol-disappearance of the difunctional monomer). The reaction mixture is filtered to remove the enzyme. The resulting solution is examined by GPC. The composition of the product is generally comprised of: 60 to 75 weight percent polyester macromer, 20 to 30 weight percent pentanediol-difunctional monomer, 0 to 10 weight percent DEMM. Add 100 ppm MEHQ and 10 ppm MSA to the final product. MSA is accurately weighed out of 1 weight percent MSA DEMM solution. The reaction is illustrated by this reaction:

  For most experiments, the composition is 60-70% polyester macromer having a molecular weight of 800, 30-35% DEMM-pentanediol bifunctional molecule, and 5-10% DEMM. Reference to the composition of the polyester refers to this general composition. If it deviates from this, it will be stated concretely.

Example 6: Test of polyester composition on cold rolled steel

  The cold-rolled steel plate is made of Q-Panel (4 ′ ′ × 6 ′ ′ steel plate). Steel plates require an initiator to be bonded to a substrate for use. Pyridylethyltrimethoxysilane (PETS) and branched polyethyleneimine (PEI) are used as initiators as a 1% solution in butyl cellosolve. The initiator solution was drawn down using a # 2.5 Meyer rod and the solvent was allowed to evaporate at 80 ° C. for 5 minutes. Drawing down a solution of the polyester composition using a # 20 Meyer rod gives a wet film thickness of 40 microns. The curing temperature used is 80.degree. Allow the coated panel to cure within 20-30 minutes. The properties of the coatings obtained after full curing are summarized in Table 2. In order to pass the crosshatch test, the result must be 5B. In order to pass the mandrel test, it is necessary that the sample does not show any cracks detected at all bending angles on the mandrel.

  A polyester composition having a molecular weight of 800 is also cured using a branched PEI initiator having a molecular weight of 800. The results of the study are summarized in Table 3. The improved flexibility of the polyester composition in the mandrel test results from the higher molecular weight of the polyester composition.

Example 7 Spray Coating on Base Coated Steel Sheet

  Professionally spray the BASF R-M Onyx HDTM basecoat onto the plate. There is some variation in the color of the coated basecoat between the different tests. This demonstrates the robustness of the chemical reaction that it can be cured on different color base coats.

  The clearcoat is also sprayed onto the basecoated plate. Each formulation is sprayed using an automotive refinish HVLP gun (Anest Iwata model number WS-400). Each round of spraying takes place in a forced ventilation laboratory hood with an air flow of 100 ft / min. Before use for the first time, pacify the gun by spraying a solution of 1% methanesulfonic acid in acetone. The gun is connected to a 90 psi store compressed air source and it is lowered to 25 psi at gauge pressure using a regulator. During spraying, the operating pressure reading is 20 psi. Apply 2 spray coatings so that each pass is 50% overlapping on top of one another. After each formulation, clean the gun by spraying acetone twice through the gun.

  The polyester composition is prepared by the formulation according to Table 4 below. BYK 333 is a polyether modified silicone additive used to improve basecoat wet out. The polyester composition is diluted using 40% butyl cellosolve solvent to improve sprayability and aid wet out. Formulation 1 using polyester and solvent comprises a polyester composition having a molecular weight of 60 weight percent, 0.1 weight percent BYK 333 polyether modified silicone, and 40 weight percent butyl cellosolve.

  This demonstrates that good coatability is obtained when the polyester-based formulation is cured at high temperature using a base coat.

Example 8: Example 7 is repeated except that the selected curing temperature is 82 ° C. The properties of the resulting coating are not affected as shown in Table 6 below.

Example 9: Replacement of solvent with reactive diluent (DEMM)

  20% of DEMM (dimethyl methylene malonate) is added to reduce the weight percentage of butyl cellosolve to 20 percent. DEMM reacts rapidly to form crosslinks with difunctional and multifunctional components at lower temperatures. The formulation comprises 60 weight percent polyester macromer having a molecular weight of 800, 0.1 weight percent BYK 333 polyether modified silicone, 20 weight percent butyl cellosolve, and 20 weight percent DEMM.

The coating procedure is similar to that described in Example 6. Curing the coating at 50 ° C. for 25 minutes results in complete cure. The coating looked beautiful and exhibited good properties as shown in Table 7.

Acid and base resistance tests are conducted using the GM method, GMW 14701. The results are summarized in Table 8.

  This demonstrates that the coating has good acid and base resistance after complete crosslinking, and failure occurs only at high temperatures.

Example 10: Formulation with polyester and acrylic polyol

  Acrylic polyols are selected and used in varying amounts with the polyester to improve flexibility, resistance, and long term aging characteristics. An acrylic polyol made by BASF under the tradename Joncryl and one made by Dow under the tradename Paraloid are utilized. Several formulations were made to determine the ratio of acrylic polyol to polyester to provide the desired flexibility and to improve the paintability. Two ratios of polyester to acrylic polyol are selected based on cure speed and conditions and evaluation of paintability after cure. The basecoat is coated as described above and the formulation is sprayed onto a hardened steel plate.

  The formulation may be cured using anionic polymerization and Michael addition reaction. As the hydroxyl groups present on the surface of the basecoat and scattered throughout the chain length of the acrylic polyol undergo a Michael addition reaction with the reactive methylene groups present in the polyol, the polyol is incorporated into the crosslinked matrix.

  Spray Coating Formulation 3 onto Car Star Base Coat

Example 11
Formulation 4 is spray coated onto a Car Star base coat. Formulation 4 is shown in the mandrel test to be less flexible.

  From Example 11, a coating made using Formulation 4 is resistant to 168 hours for accelerated testing using UV / moisture exposure, and against corrosion due to salt spray exposure It is clearly stated that it has a tolerance of 168 hours.

Example 12: Use of other polyesters in the formulation

  A polyester according to the following structure prepared from pentanediol and DEM is used in formulation 5 described below.

  The spraying and curing process is as described in the above examples. Longer cure times are required, due to the diminished electron withdrawing ability of the methylene group due to the spaced effects. The paintability after full curing can be summarized in Table 14 below.

Cure time 25 minutes @ 60 ° C, followed by 15 minutes @ 120 ° C

  Formulation 5 has much better flexibility in mandrel testing due to the spaced structure of the base polyester. Its pencil hardness before aging is low. After UV / moisture and salt spray testing, the formulation can maintain its gloss, adhesion, and flexibility. Thus, spacing the methylene groups in the polyester can provide a useful strategy to improve flexibility after tolerance testing, but initial testing should reflect the best possible combination of properties. It has not been done.

Example 13: Coating made of polyester with cyclic structure

The inclusion of a cycloaliphatic ring in the diol to make the polyester by using a diol such as cyclohexanedimethanol (CDM) reduces the free volume in the system, resulting in overall moisture and UV resistance Is improved and the resulting polymer is given rigidity. The structure of polyester is as shown in the following chemical formula.

  The spraying and curing process is as described in the above examples. Longer cure times are required due to the reduced electron withdrawing ability of the methylene group due to the CDM group. The paintability after full curing can be summarized in Table 16 below.

  Cure time 25 minutes @ 60 ° C, followed by 15 minutes @ 120 ° C

  Formulation 6 demonstrates a lower flexibility in mandrel testing due to the cyclic structure of the base polyester. The pencil hardness before aging becomes high. After UV / moisture and salt spray testing, this formulation can maintain its gloss and adhesion. The formulation can maintain 100% gloss even after exposure to 99% relative humidity for 3 weeks in a humidity room. This indicates an improvement in moisture resistance due to the cyclic structure present in the polyester.

  Parts by weight as used herein are based on the 100 parts by weight of the composition specifically mentioned. Any numerical value listed in the specification above will have all values from the lower limit to the upper limit, in 1-unit increments, provided there is a gap of at least 2 units between any lower limit and any upper limit. Including. By way of example, the amounts of constituents or the values of process variables, such as temperature, pressure, time etc., are for example stated as 1 to 90, preferably 20 to 80, more preferably 30 to 70 Values such as 85, 22-68, 43-51, 30-32 etc. are intended to be explicitly listed herein. For numbers less than one, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. These are only examples of what is specifically intended, and all possible combinations between the listed minimum and maximum values should likewise be considered as explicitly described herein. . Unless otherwise stated, all ranges include both endpoints and all numbers between the endpoints. The use of "about" or "approximately" in connection with a range applies to both ends of the range. Thus, "about 20-30" is intended to cover "about 20 to about 30", including at least the designated end points. The term "consisting essentially of" describing a combination does not substantially affect the basic and novel properties of the identified element, component, component or step, and combination. It is intended to include elements, ingredients, components or steps. The use of the term "comprising" or "including" in combination herein with elements, ingredients, components or steps refers to the elements, ingredients, components or steps An embodiment essentially consisting of is also contemplated. Multiple elements, components, components or steps may be represented by a single integrated element, component, component or step. Alternatively, a single integrated element, component, component or step may be divided into separate multiple elements, components, components or steps. The disclosure “a” or “one” describing an element, ingredient, component, or step is intended to exclude additional elements, ingredients, components, or steps. Absent.

Claims (30)

a) A polyester macromer composition comprising one or more polyester macromers containing one or more chains of residues of one or more diols and one or more diesters, said one or more diols and The residues of one or more diesters alternate along the chain, wherein a portion of the diesters is 1,1-diester-1-alkene and at least one end is the 1,1-diester-1 Said polyester macromer composition comprising one residue of an alkene, wherein one or more of the ends may comprise one or more residues of a diol; and b) one or more having a pendant Michael addition reaction donor group A composition comprising a polymer.   The composition according to claim 1, wherein the pendant Michael addition reaction donating group comprises a functional group containing an active hydrogen atom.   The composition according to claim 1 or 2, wherein the pendant Michael addition reaction donating group comprises an amine, a hydroxyl, a thiol, or a mixture thereof.   The composition contains one or more chains of alternating residues of one or more diols and one or more diesters, each of the chains being the remainder of a polyol having three or more oxygen atoms. A composition according to any one of the preceding claims, which is attached at one end to the group oxygen. The polyester macromer corresponds to formula 1

Wherein Z is -R ² OH or -R ¹ separately at each occurrence;
R ¹ is a hydrocarbyl group which may contain one or more heteroatoms, each occurrence of which is separate;
R ² is a hydrocarbylene group having two or more bonds to an oxygen atom, each occurrence separately, said hydrocarbylene group may contain one or more heteroatoms;
c is an integer of 1 or more;
n is an integer of about 1 to 3;
The composition according to any one of claims 1 to 4.   6. The composition of any one of the preceding claims, wherein c is an integer of about 3 to about 6.   The one or more polymers having the pendant type Michael addition reaction donating group include one or more of an acrylic polyol, an amine modified acrylic polyol, a polycarbonate polyol, a modified acrylic copolymer polyol, a polyester polyol, a polyether polyol, and a siloxane polyol Composition according to any of the preceding claims.   The composition according to any one of the preceding claims, wherein the one or more polymers having pendant Michael addition reaction donating groups comprise one or more acrylic polyols or amine modified acrylic polyols.   a) about 40 to about 90 weight percent of one or more polyester macromers, and about 10 to 60 weight percent of one or more polymers having one or more pendant Michael addition reaction donor groups, the amount being A composition according to any one of the preceding claims, based on the weight of the composition.   10. The composition of claim 9, comprising a solvent comprising one or more polar aprotic solvents.   11. The composition of claim 10, wherein the solvent comprises one or more alkylene glycol ethers, acetate modified alkylene glycol ethers, or ketones having a boiling point of about 80 <0> C to about 200 <0> C.   12. The composition according to any one of claims 10 or 11, wherein the solvent is present in an amount of about 5 to about 30 weight percent and the amount is based on the weight of the composition.   The composition according to any one of the preceding claims, wherein the polyester macromer exhibits a number average molecular weight of about 600 to about 3000.   The composition according to any one of the preceding claims, wherein the one or more chains of the polyester macromer comprise residues of one or more dihydrocarbyl dicarboxylates.   15. The composition of claim 14, wherein the one or more dihydrocarbyl dicarboxylates comprise one or more of aromatic dicarboxylates, aliphatic dicarboxylates, and alicyclic dicarboxylates. The polyol used to prepare the polyester macromer corresponds to the following formula:

The 1,1-diester-1-alkene corresponds to the following formula:

The one or more dihydrocarbyl dicarboxylates correspond to the formula:

In which R ¹ is a hydrocarbyl group which may contain one or more heteroatoms, each occurrence separately;
R ² is a hydrocarbylene group having two or more bonds to an oxygen atom, each occurrence separately, which hydrocarbylene group may contain one or more heteroatoms; c Is an integer of 2 or more;
R ³ is a hydrocarbylene group having two bonds to the carbonyl group of the diester separately, each occurrence, and the hydrocarbylene group may contain one or more heteroatoms;
c is an integer of 1 or more,
A composition according to any one of the preceding claims. The polyester macromer corresponds to the following formula:

Where D corresponds to

Z is -R ² OH or -R ¹ separately at each occurrence;
R ¹ is a hydrocarbyl group which may contain one or more heteroatoms, each occurrence of which is separate;
R ² is a hydrocarbylene group having two or more bonds to an oxygen atom, each occurrence separately, said hydrocarbylene group may contain one or more heteroatoms;
R ³ is a hydrocarbylene group having two bonds to the carbonyl group of the residue of the diester separately, as and when they occur, the hydrocarbylene group containing one or more heteroatoms Also well;
c is an integer of 1 or more;
n is an integer of about 1 to 3;
p is an integer of 1 or more;
q is an integer of 1 or more,
A composition according to any one of the preceding claims.   The composition according to any one of the preceding claims, wherein about 1 to about 4 dihydrocarbyl dicarboxylates are contained in each chain. The polyester macromer composition is
i) multiple polyester macromers;
ii) one or more multifunctional monomers containing residues of one or more polyols and one or more 1,1-diester-1-alkenes, the hydroxyl group of said polyol of said multifunctional monomer Said multifunctional monomer, wherein substantially all of said 1, 1-diester 1-alkene is replaced by said 1, 1-diester 1-alkene; and iii) one or more 1, 1-diester 1-alkenes The composition according to any one of the preceding claims. The polyester macromer composition is
i) about 10 to about 90 weight percent of multiple polyester macromers;
ii) about 1 to about 50 percent by weight of one or more multifunctional monomers; and iii) about 1 to about 30 percent by weight of one or more 1,1-diester-1-alkenes,
The percentage is based on the amount of said listed components,
A composition according to claim 9.   The composition according to any one of the preceding claims, wherein the polymer having pendant Michael donating groups exhibits a hydroxyl number of about 50 to about 200.   The composition according to claim 1, which is cured in the form of a coating.   23. The composition of claim 22, which is a coating having a thickness of about 1 to about 160 microns.   Any of the preceding claims, wherein the polyester macromer is crosslinked by a Michael addition reaction to the one alkene group of the Michael addition reaction donor suspended through the 1,1-alkene group and / or from the polymer. The composition according to item 1.   The cured coating has the following properties: gloss according to ASTM D523-08, gloss of 40 GU or more at 20 ° or 60 ° or 85 °; pencil hardness of 3 H or more according to ASTM D3363-00; ASTM D5402-93 Methyl ethyl ketone friction 80 or more solvent resistance; 80% or more mandrel flexibility according to ASTM D522-93; 4B or more and 100% crosshatch adhesion according to ASTM D 3359-09, and acid resistance up to 70 ° C according to GMW 14701 25. The composition according to any of claims 22-24, which exhibits one or more of the following properties: base and resistance above 70 <0> C.   22. Contacting the composition according to any one of claims 1 to 21 with the surface of a substrate which is at least weakly nucleophilic, and said one or more polyesters on said surface of said substrate Forming a coating comprising said composition containing a macromer.   27. The method of claim 26, wherein the substrate has a pigmented coating deposited on its surface, and the pigmented coating is weakly basic or nucleophilic.   Said substrate comprising said composition comprising one or more polyester macromers deposited on said substrate is crosslinked by said coating comprising one or more polyester macromers disposed on said surface of said substrate 27. The method of claim 26, comprising exposing to a temperature of about 20 <0> C to about 150 <0> C for about 10 minutes to about 120 minutes under such conditions.   27. The method of claim 26, wherein the coating or the surface of the substrate contains a catalyst for a Michael addition reaction.   27. The method of claim 26, wherein the coating on the surface of the substrate comprises an initiator for anionic polymerization.